Guidance on the Application of the CLP Criteria

DRAFT Guidance on the Application of the CLP Criteria

(Public) DRAFT Version 5.0 – July 2016 1

G U I D A N C E

Guidance on the Application of the CLP Criteria

Guidance to Regulation (EC) No 1272/2008 on classification, labelling

and packaging (CLP) of substances and mixtures

(Public) Draft Version 5.0

July 2017

2


(Public) DRAFT Version 5.0 – July 2016

Legal Notice

This document aims to assist users in complying with their obligations under the CLP

Regulation. However, users are reminded that the text of the CLP Regulation is the only

authentic legal reference and that the information in this document does not constitute legal

advice. Usage of the information remains under the sole responsibility of the user. The

European Chemicals Agency does not accept any liability with regard to the use that may be

made of the information contained in this document.

Guidance on the Application of CLP Criteria

Reference: ECHA-xx-x-xx-EN

ISBN: xxx-xx-xxxx-xxx-x

Publ.date: xxxx 2017

Language: EN

© European Chemicals Agency, 2016

If you have questions or comments in relation to this document please send them (indicating

the document reference, issue date, chapter and/or page of the document to which your

comment refers) using the Guidance feedback form. The feedback form can be accessed via

the ECHA Guidance website or directly via the following link:

https://comments.echa.europa.eu/comments_cms/FeedbackGuidance.aspx

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Document History 1

Version Comment Date

n.a. First edition August 2009

n.a. Please note that change between the version published in

August 2009 and that of April 2011 are not recorded in this

document history.

April 2011

Version 2.0 Revision of the Guidance addressing content in relation to the

environmental criteria chapters and Annexes following the 2nd

Adaptation to Technical Progress to the CLP Regulation

(Commission Regulation (EU) No 286/2011). The ECHA

Secretariat revised the Guidance Part 4 – Environmental

hazards and Annexes of the guidance document referring to

the revised criteria for the long-term aquatic hazard for

substances and mixtures and added new Part 5 – Additional

hazards referring to the hazard class ‘hazardous to the ozone

layer’. As well, a number of examples have been included in

the respective Parts and Annexes to illustrate the revisions

performed. Further to this, a range of editorial corrections were

proposed for Part 1- General principles for classification and

labelling.

The update includes the following:

Revision of Part 1, by eliminating and amending out of

date information and restructuring the text in order to

reflect the Guidance update.

All green boxes in Part 4 that are impacted by the 2nd

ATP were updated. As the CLP legal text uses commas

instead of dots to define numbers smaller than 1, the

green boxes now show commas as well.

Revision of Part 4, by providing guidance on the

application of the new long-term aquatic hazard criteria

for substances and mixtures.

Section 4.1.3 Classification of substances hazardous to

the aquatic environment and section 4.1.4 Classification

of mixtures hazardous to the aquatic environment were

substantially revised, for example by addition of new

references, as well as the new/ revised examples to

illustrate relevant topics in the Part 4.

New Part 5 - Additional hazards was added (please note

that Part 5: Labelling was deleted from the Guidance in

previous non recorded versions and covered via a new

Guidance on Labelling and Packaging in accordance with

Regulation (EC) No 1272/2008 published in April 2011).

Most of the I.3 sub-sections in Annex I – Aquatic toxicity

were revised.

April 2012

4


(Public) Draft version 5.0 – July 2016

In Annex II – Rapid degradation the terminology was

modified.

Most of the Annex IV – Metals and Inorganic Metal

Compounds was substantially modified and revised, as

well as in sub-section IV.7 new examples were added.

Version 3.0 Revision of Guidance Part 3 Health Hazards, relating to specific

concentration limits (SCLs) for 4 hazard classes and the

inclusion of a new Annex.

The update includes the following:

Revision of Part 3, by providing guidance on the setting

of lower and higher SCLs for 4 health hazard classes in

section 3.2.2.5 Skin Corrosion/Irritation; section 3.3.2.5

Serious Eye Damage/Eye Irritation; section 3.7.2.5

Reproductive Toxicity and section 3.8.2.6 STOT-SE, in

accordance with CLP Article 10(7);

Inclusion of a new Annex (Annex VI) providing guidance

on setting SCLs for the reproductive toxicity hazard class

based on potency considerations.

November

2012

Version 4.0 (i) Revision of the CLP Guidance addressing content in

relation to the Part 2: Physical hazards, Part 3: Health

hazards and Annex VI following the 2nd and the 4th

Adaptation to Technical Progress to the CLP Regulation

(Commission Regulation (EU) No 286/2011 of 10 March

2011 and Commission Regulation (EU) No 487/2013 of 8

May 2013).

The revision includes:

Numbering of chapters within CLP Guidance, Parts 2 & 3

were synchronised with corresponding chapter

numbering of CLP, Annex I.

Changes in the legal text due the 2nd and 4th ATPs.

Changes in the legal text due to the 4th ATP were

highlighted in orange within all relevant green boxes. All

changes are preceded by a note highlighting the

changes. (To note: a corrigendum will change the colour

of relative legal text boxes from orange to green when

the 4th ATP applies).

In addition, the revisions to Part 2: Physical hazards include

the following:

Chapters ‘Pyrophoric liquids and solids’ and ‘Oxidising

liquids and solids’ were divided into four chapters:

‘Pyrophoric liquids’, ‘Pyrophoric solids’, ‘Oxidising liquids’

and ‘Oxidising solids’ respectively.

Based on the 4th ATP the CLP Guidance Chapter 2.2

Flammable gases was extended to take into account the

scope of CLP, Annex I, section 2.2 to include chemically

unstable gases.

November

2013


(Public) Draft version 5.0 – July 2016 5

Further, the 4th ATP amended the criteria in CLP Annex

I, Section 2.3 Flammable aerosols and renamed it into

2.3 Aerosols. Hence, the CLP Guidance was amended

accordingly.

All chapters were rechecked and redundant and/or

outdated information were deleted, reorganised and/or

revised. For example, ‘Introduction’ chapters were

significantly shortened, however several “examples”

sections (i.e. ‘Example for classification…’) were further

elaborated.

Where missing, a new sub-chapter ‘Relation to other

physical hazards’ was added.

Sub-chapter 2.0.4 ‘Physical state’ was extended with

additional information about substance/mixture form

and some examples.

In sub-chapter 2.1.5.2 ‘Additional labelling provisions’

within chapter 2.1 ‘Explosives’ further guidance about

hazard communication was provided.

In sub-chapter 2.5.6.1 a new recommendation for shot

hazard codes to identify the classification of gasses

under pressure was added.

Footnotes with references to endorsed or on-going

revisions of the GHS which have not yet been

implemented into the CLP via a respective ATP were

included in relevant sub-chapters of this guidance for

information only.

In addition, the major revisions to Part 3: Health hazards

include the following:

All sections: revisions to legal text for the 4th ATP,

including revisions to Precautionary Statements in the

Tables with labelling information

Section 3.1: the introduction of new guidance for the 4th

ATP in section 3.1.4.1

Sections 3.22.5 and 3.3.2.5: clarification to the recently

published text (Version 3.0) for the setting of SCLs.

Section 3.4 (sensitisation) has been significantly re-

organised to present all the information on respiratory

sensitisation together, followed by the information on

skin sensitisation. This is in line with how the sections

are presented in the CLP Regulation and in GHS

documents.

Section 3.4: integration of subcategories for respiratory

and skin sensitisation based on potency of a substance;

clarification of semi-quantitative terms like ‘low to

moderate sensitisation rate’ and ‘high or low exposure’;

6



elaboration of evlauation of human data for skin

sensitisation and the addition of new examples.

Section 3.7 the introduction of new guidance for the 4th

ATP in section3.7.4.1 and section 3.7.5.1.

(ii) Corrigendum of Part 1: General principles for

classification and labelling and Part 4: Environmental

hazards and its related Annexes I-V.

The corrigendum includes the following:

The list of abbreviations was updated.

Update or deletion of outdated references to Guidance

on information requirements and chemical safety

assessment, Endpoint specific guidance (Chapter R.7a)

within Annexes I-V.

A footnote informing the reader that with effect from 1

September 2013, Directive 98/8/EC had been repealed

by Biocidal Products Regulation (EU) No 528/2012 was

added.

In Part 1, Part 4 and Annexes modal verbs ‘shall’ were

replaced with ‘must’ where appropriate.

A footnote related to respiratory sensitisation and skin

sensitisation in Table 1.5.1-a was removed.

A correction to Example D, sub-chapter 4.1.4.7.5 was

applied, namely a reference to CLP, Annex I, point (b)

(ii) of Table 4.1.0 was introduced. In addition the result

of a summation method calculation was corrected.

Version 4.1

Corrigendum to take account of the end of the transition period

of the 4th ATP (as foreseen in version 4.0 above):

change the colour of relative legal text boxes from

orange to green;

in Part 2, to delete section 2.2.1 Flammable gases and

section 2.3.1 Flammable Aerosols (outdated text) and

renumber sections 2.2.2 Flammable gases (including

chemically unstable gases)and 2.3.2 Aerosols

accordingly;

in Part 3, to delete the “outdated text” in sections

3.7.4.1 and 3.7.5.1 in Reproductive Toxicity.

In addition, minor editorial errors were corrected and minor

reformatting was made.

June 2015

Version 5.0 [See draft updated PART 1] Xxxx 2017

1



Preface 1

2

[See draft updated text in PART 1] 3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

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1

Table of Contents 2

1. PART 1: GENERAL PRINCIPLES FOR CLASSIFICATION AND 3

LABELLING .................................................................................... 17 4

1.1. INTRODUCTION ...................................................................................... 17 5

1.2. THE SIGNIFICANCE OF THE TERMS ‘FORM OR PHYSICAL STATE’ AND 6

‘REASONABLY EXPECTED USE’ WITH RESPECT TO CLASSIFICATION 7

ACCORDING TO CLP................................................................................ 17 8

1.3. SPECIFIC CASES REQUIRING FURTHER EVALUATION – LACK OF 9

BIOAVAILABILITY ................................................................................... 17 10

1.4. USE OF SUBSTANCE CATEGORISATION (READ ACROSS AND GROUPING) AND 11

(Q)SARS FOR CLASSIFICATION AND LABELLING ........................................ 17 12

1.5. SPECIFIC CONCENTRATION LIMITS AND M-FACTORS.................................. 17 13

1.6. MIXTURES ............................................................................................. 17 14

1.7. THE APPLICATION OF ANNEX VII .............................................................. 17 15

1.7.1. 17 16

2. PART 2: PHYSICAL HAZARDS ......................................................... 18 17

2.0. INTRODUCTION ...................................................................................... 18 18

2.0.1 General remarks about the prerequisites of classification and testing .................... 18 19

2.0.2 Safety ........................................................................................................... 18 20

2.0.3 General conditions for testing .......................................................................... 18 21

2.0.4 Physical state ................................................................................................. 19 22

2.0.5 Quality .......................................................................................................... 19 23

2.1. EXPLOSIVES .......................................................................................... 20 24

2.1.1. Introduction ................................................................................................... 20 25

2.1.2. Definitions and general considerations for the classification of explosives .............. 20 26

2.1.3. Relation to other physical hazards .................................................................... 21 27

2.1.4. Classification of substances, mixtures or articles as explosives ............................. 22 28

2.1.4.1. Identification of hazard information ............................................................ 22 29

2.1.4.2. Screening procedures and waiving of testing ................................................ 22 30

2.1.4.3. Classification criteria ................................................................................. 23 31

2.1.4.4. Testing and evaluation of hazard information ............................................... 25 32

2.1.4.5. Classification procedure and decision logics ................................................. 25 33

2.1.4.5.1. Acceptance procedure ......................................................................... 27 34

2.1.4.5.2. Assignment procedure to a division ....................................................... 29 35

2.1.5. Hazard communication for explosives................................................................ 34 36

2.1.5.1. Pictograms, signal words, hazard statements and precautionary statements .... 34 37

2.1.5.2. Additional labelling provisions .................................................................... 35 38

2.1.5.3. Further communication requirements .......................................................... 37 39

2.1.6. Relation to transportclassification ..................................................................... 37 40

2.1.7. Examples of classification for explosives ............................................................ 37 41

2.1.7.1. Example of substances and mixtures fulfilling the classification criteria ............ 38 42

2.1.7.2. Example of substances and mixtures not fulfilling the classification criteria ...... 39 43



2.2. FLAMMABLE GASES (INCLUDING CHEMICALLY UNSTABLE GASES) ............... 43 1

2.2.1. Introduction ................................................................................................... 43 2

2.2.2. Definitions and general considerations for the classification of flammable gases 3

(including chemically unstable gases) ............................................................... 43 4


2.2.4. Classification of substances and mixtures as flammable gases (including chemically 6

unstable gases) .............................................................................................. 43 7


2.2.4.2. Screening procedures and waiving of testing for gas mixtures ........................ 44 9



2.2.4.5. Decision logic ........................................................................................... 46 12

2.2.4.5.1. Decision logic for flammable gases ........................................................ 47 13

2.2.4.5.2. Decision logic for chemically unstable gases ........................................... 48 14

2.2.5. Hazard communication for flammable gases (including chemically unstable gases) . 49 15


2.2.6. Relation to transport classification .................................................................... 50 17

2.2.7. Example of classification for flammable gases .................................................... 50 18

2.3. AEROSOLS ............................................................................................. 52 19

2.3.1. Introduction ................................................................................................... 52 20

2.3.2. Definitions and general considerations for the classification of aerosols ................. 52 21


2.3.4. Classification of aerosols ................................................................................. 53 23



2.3.4.3. Decision logic ........................................................................................... 54 26

2.3.4.3.1. Decision logic for aerosols .................................................................... 55 27

2.3.4.3.2. Decision logic for spray aerosols ........................................................... 56 28

2.3.4.3.3. Decision logic for foam aerosols ............................................................ 57 29

2.3.5. Hazard communication for aerosols .................................................................. 58 30


2.3.5.2. Additional labelling provisions .................................................................... 58 32


2.3.7. Examples of classification for aerosols ............................................................... 59 34

2.3.7.1. Examples of aerosols fulfilling the classification criteria ................................. 59 35

2.3.7.2. Examples of aerosols not fulfilling the classification criteria ............................ 60 36

2.4. OXIDISING GASES.................................................................................. 61 37

2.4.1. Introduction ................................................................................................... 61 38

2.4.2. Definitions and general considerations for the classification of oxidising gases ........ 61 39


2.4.4. Classification of substances and mixtures as oxidising gases ................................ 61 41





2.4.4.5. Decision logic ........................................................................................... 62 46

2.4.5. Hazard communication for oxidising gases ......................................................... 63 47



10



2.4.7. Example of classification for oxidising gases....................................................... 64 1

2.4.7.1. Example of substances and mixtures not fulfilling the classification criteria ...... 64 2

2.5. GASES UNDER PRESSURE ........................................................................ 65 3

2.5.1. Introduction ................................................................................................... 65 4

2.5.2. Definitions and general considerations for the classification of gases under pressure5

.................................................................................................................... 65 6

2.5.2.1. Definition of ‘gas’ ...................................................................................... 65 7

2.5.2.2. Definition of gases under pressure .............................................................. 65 8


2.5.4. Classification of substances and mixtures as gases under pressure ....................... 66 10




2.5.4.4. Decision logic ........................................................................................... 67 14

2.5.5. Hazard communication for gases under pressure ................................................ 69 15



2.5.7. Examples of classification for gases under pressure ............................................ 71 18

2.5.7.1. Examples of substances and mixtures fulfilling the classification criteria .......... 71 19

2.5.7.1.1. Example mixture: 9 % (O2) + 16 % (N2O) + 75 % (N2) .......................... 71 20

2.6. FLAMMABLE LIQUIDS .............................................................................. 72 21

2.6.1. Introduction ................................................................................................... 72 22

2.6.2. Definitions and general considerations for the classification of flammable liquids .... 72 23


2.6.4. Classification of substances and mixtures as flammable liquids ............................ 72 25



2.6.4.2.1. Boiling point ....................................................................................... 72 28

2.6.4.2.2. Flash point ......................................................................................... 73 29



2.6.4.4.1. Testing .............................................................................................. 74 32

2.6.4.4.2. Evaluation of hazard information .......................................................... 75 33

2.6.4.5. Decision logic ........................................................................................... 75 34

2.6.5. Hazard communication for flammable liquids ..................................................... 77 35


2.6.5.2. Additional labelling provisions for flammable liquids ...................................... 77 37

2.6.6. Re-classification of substances and mixtures classified as flammable liquids 38

according to DSD and DPD or already classified for transport ............................... 78 39

2.6.6.1. Relation to transport classification .............................................................. 78 40

2.6.7. Examples of classification for flammable liquids .................................................. 78 41


2.6.7.1.1. Example 1 ......................................................................................... 78 43

2.6.7.1.2. Example 2 ......................................................................................... 79 44

2.6.7.2. Examples of substances and mixtures not fulfilling the classification criteria ..... 79 45

2.6.7.2.1. Example 3 ......................................................................................... 79 46

2.6.8. References .................................................................................................... 79 47

2.7. FLAMMABLE SOLIDS ............................................................................... 80 48

2.7.1. Introduction ................................................................................................... 80 49



2.7.2. Definitions and general considerations for the classification of flammable solids ..... 80 1


2.7.4. Classification of substances and mixtures as flammable solids .............................. 81 3





2.7.4.5. Decision logic ........................................................................................... 82 8

2.7.5. Hazard communication for flammable solids ...................................................... 84 9



2.7.7. Examples of classification for flammable solids ................................................... 84 12

2.7.7.1. Example of substances and mixtures fulfilling the classification criteria ............ 84 13

2.7.7.2. Examples of substances and mixtures not fulfilling the classification criteria ..... 85 14

2.7.8. References .................................................................................................... 85 15

2.8. SELF-REACTIVE SUBSTANCES AND MIXTURES ........................................... 86 16

2.8.1. Introduction ................................................................................................... 86 17

2.8.2. Definitions and general considerations for the classification of self-reactives .......... 86 18


2.8.4. Classification of substances and mixtures as self-reactive .................................... 87 20




2.8.4.3.1. Thermal stability tests and temperature control ...................................... 89 24

2.8.4.3.2. Additional considerations and testing .................................................... 90 25

2.8.4.3.3. Additional classification considerations .................................................. 91 26

2.8.4.4. Decision logic ........................................................................................... 92 27

2.8.5. Hazard communication for self-reactives ........................................................... 94 28


2.8.6. Relation to transport classificationaccording to DSD and DPD or already classified 30

for transport .................................................................................................. 95 31

2.8.7. Examples of classification for self-reactives ........................................................ 95 32


2.9. PYROPHORIC LIQUIDS ............................................................................ 99 34

2.9.1. Introduction ................................................................................................... 99 35

2.9.2. Definitions and general considerations for the classification pyrophoric liquids ........ 99 36


2.9.4. Classification of substances and mixtures as pyrophoric liquids .......................... 100 38

2.9.4.1. Identification of hazard information .......................................................... 100 39

2.9.4.2. Screening procedures and waiving of testing .............................................. 100 40

2.9.4.3. Classification criteria ............................................................................... 100 41

2.9.4.4. Testing and evaluation of hazard information ............................................. 100 42

2.9.4.5. Decision logic ......................................................................................... 101 43

2.9.4.5.1. Decision logic for pyrophoric liquids .................................................... 102 44

2.9.5. Hazard communication for pyrophoric liquids ................................................... 103 45

2.9.5.1. Pictograms, signal words, hazard statements and precautionary statements .. 103 46

Relation to transport classification .......................................................................... 103 47

2.9.6. 103 48

2.9.7. Examples of classification for pyrophoric liquids ................................................ 104 49

12



2.9.7.1. Examples of substances and mixtures fulfilling the classification criteria ........ 104 1

2.9.7.1.1. Example 1 ....................................................................................... 104 2

2.9.7.1.2. Example 2 ....................................................................................... 105 3

2.9.7.2. Examples of substances and mixtures not fulfilling the classification criteria ... 105 4

2.9.7.2.1. Example 3 ....................................................................................... 105 5

2.9.8. References .................................................................................................. 105 6

2.10. PYROPHORIC SOLIDS .............................................................................106 7

2.10.1. Introduction ................................................................................................. 106 8

2.10.2. Definitions and general considerations for the classification pyrophoric solids ....... 106 9

2.10.3. Relation to other physical hazards .................................................................. 107 10

2.10.4. Classification of substances and mixtures as pyrophoric solids ........................... 107 11





2.10.4.5. Decision logic ......................................................................................... 108 16

2.10.4.5.1. Decision logic for pyrophoric solids ..................................................... 109 17

2.10.5. Hazard communication for pyrophoric solids .................................................... 109 18



2.10.6. 110 21

2.10.7. Examples of classification for pyrophoric solids ................................................. 110 22


2.10.7.1.1. Example 1 ....................................................................................... 110 24

2.10.7.1.2. Example 2 ....................................................................................... 110 25


2.10.7.2.1. Example 3 ....................................................................................... 110 27

2.10.7.2.2. Example 4 ....................................................................................... 111 28

2.10.8. References .................................................................................................. 111 29

2.11. SELF-HEATING SUBSTANCES AND MIXTURES ...........................................112 30

2.11.1. Introduction ................................................................................................. 112 31

2.11.2. Definitions and general considerations for the classification of self-heating 32

substances and mixtures ............................................................................... 112 33


2.11.4. Classification of self-heating substances and mixtures ....................................... 112 35





2.11.4.4.1. General remarks ............................................................................... 114 40

2.11.4.4.2. Sample preparation .......................................................................... 114 41

2.11.4.4.3. Criteria and evaluation ...................................................................... 114 42

2.11.4.5. Decision logic ......................................................................................... 115 43

2.11.4.6. Exemption ............................................................................................. 116 44

2.11.5. Hazard communication for self-heating substances and mixtures ........................ 118 45



2.11.6. 118 48

2.11.7. Examples of classification for self-heating substances and mixtures .................... 119 49





2.11.8. References .................................................................................................. 120 3

2.12. SUBSTANCES AND MIXTURES WHICH, IN CONTACT WITH WATER, EMIT 4

FLAMMABLE GASES ................................................................................121 5

2.12.1. Introduction ................................................................................................. 121 6

2.12.2. Definitions and general considerations for the classification of substances and 7

mixtures which, in contact with water, emit flammable gases ............................ 121 8


2.12.4. Classification of substances and mixtures which, in contact with water, emit 10

flammable gases .......................................................................................... 122 11





2.12.4.4.1. Testing procedure ............................................................................. 124 16

2.12.4.4.2. Evaluation of hazard information ........................................................ 125 17

2.12.4.5. Decision logic ......................................................................................... 125 18

2.12.5. Hazard communication for substances and mixtures which, in contact with water, 19

emit flammable gases ................................................................................... 127 20

2.12.5.1. Pictograms, signal words, hazard statements and precautionary statements for 21

substances and mixtures ......................................................................... 127 22

2.12.5.2. Additional labelling provisions .................................................................. 127 23


2.12.6. 128 25

2.12.7. Examples of classification for substances and mixtures which, in contact with water, 26

emit flammable gases ................................................................................... 128 27

2.12.7.1. Example of a substance fulfilling the classification criteria ............................ 128 28

2.12.7.1.1. Example 1 ....................................................................................... 128 29

2.12.7.2. Example of a substance not fulfilling the classification criteria ...................... 130 30

2.12.7.2.1. Example 2 ....................................................................................... 130 31

2.12.8. References .................................................................................................. 130 32

2.13. OXIDISING LIQUIDS ..............................................................................131 33

2.13.1. Introduction ................................................................................................. 131 34

2.13.2. Definitions and general considerations for the classification of oxidising liquids..... 131 35


2.13.4. Classification of substances and mixtures as oxidising liquids ............................. 132 37


2.13.4.1.1. Screening procedures and waiving of testing ........................................ 132 39



2.13.4.4. Decision logic ......................................................................................... 134 42

2.13.4.5. Hazard communication for oxidising liquids ................................................ 136 43

2.13.4.5.1. Pictograms, signal words, hazard statements and precautionary statements44

...................................................................................................... 136 45

2.13.5. Relation to transport classification .................................................................. 136 46

2.13.6. Examples of classification for oxidising liquids .................................................. 137 47



14



2.13.7. Reference .................................................................................................... 137 1

2.14. OXIDISING SOLIDS ...............................................................................138 2

2.14.1. Introduction ................................................................................................. 138 3

2.14.2. Definitions and general considerations for the classification of oxidising solids ...... 138 4


2.14.4. Classification of substances and mixtures as oxidising solids .............................. 139 6


2.14.4.1.1. Screening procedures and waiving of testing ........................................ 139 8



2.14.4.4. Decision logic ......................................................................................... 142 11

2.14.4.5. Hazard communication for oxidising solids ................................................. 144 12

2.14.4.5.1. Pictograms, signal words, hazard statements and precautionary statements13

...................................................................................................... 144 14


2.14.5. 144 16

2.14.6. Examples of classification for oxidising solids ................................................... 145 17



2.14.7. Reference .................................................................................................... 145 20

2.15. ORGANIC PEROXIDES ............................................................................146 21

2.15.1. Introduction ................................................................................................. 146 22

2.15.2. Definitions and general considerations for the classification of organic peroxides .. 146 23


2.15.4. Classification of substances and mixtures as organic peroxides .......................... 147 25




2.15.4.3.1. Thermal stability tests and temperature control .................................... 149 29

2.15.4.3.2. Additional considerations and testing .................................................. 150 30

2.15.4.3.3. Additional classification considerations ................................................ 150 31

2.15.4.4. Decision logic ......................................................................................... 151 32

2.15.5. Hazard communication for organic peroxides ................................................... 153 33


2.15.5.2. Additional labelling provisions for organic peroxides .................................... 154 35


2.15.6. 154 37

2.15.7. Examples of classification for organic peroxides ................................................ 154 38


2.15.7.2. Additional remarks.................................................................................. 157 40

2.16. CORROSIVE TO METALS .........................................................................158 41

2.16.1. Introduction ................................................................................................. 158 42

2.16.2. Definitions and general considerations for the classification of substances and 43

mixtures corrosive to metals .......................................................................... 159 44


2.16.4. Classification of substances and mixtures as corrosive to metals ........................ 159 46







2.16.4.4.1. General considerations ...................................................................... 161 2

2.16.4.4.2. Additional notes on best practice for testing ......................................... 163 3

2.16.4.5. Decision logic ......................................................................................... 165 4

2.16.5. Hazard communication for substances and mixtures corrosive to metals ............. 166 5


2.16.6. Relation to transport classification .................................................................. 167 7

2.16.7. Examples of classification for substances and mixtures corrosive to metals .......... 167 8

2.16.7.1. Example of metal specimen plates after exposure to a corrosive mixture ....... 167 9

2.16.8. References .................................................................................................. 168 10

3. PART 3: HEALTH HAZARDS .......................................................... 169 11

3.1. ACUTE TOXICITY ...................................................................................169 12

3.2. SKIN CORROSION/IRRITATION ...............................................................170 13

3.3. SERIOUS EYE DAMAGE/EYE IRRITATION ..................................................171 14

3.4. RESPIRATORY OR SKIN SENSITISATION ..................................................172 15

3.5. GERM CELL MUTAGENICITY ....................................................................173 16

3.6. CARCINOGENICITY ................................................................................174 17

3.7. REPRODUCTIVE TOXICITY ......................................................................175 18

3.8. SPECIFIC TARGET ORGAN TOXICITY – SINGLE EXPOSURE (STOT-SE) ..........175 19

3.9. SPECIFIC TARGET ORGAN TOXICITY – REPEATED EXPOSURE (STOT-RE) ......175 20

4. PART 4: ENVIRONMENTAL HAZARDS ........................................... 176 21

4.1. HAZARDOUS TO THE AQUATIC ENVIRONMENT ..........................................176 22

5. PART 5: ADDITIONAL HAZARDS ................................................... 177 23

5.1. HAZARDOUS TO THE OZONE LAYER .........................................................177 24

ANNEXES .......................................................................................... 177 25

I ANNEX I: AQUATIC TOXICITY .....................................................................177 26

II ANNEX II: RAPID DEGRADATION ................................................................178 27

III ANNEX III: BIOACCUMULATION ..................................................................179 28

IV ANNEX IV: METALS AND INORGANIC METAL COMPOUNDS .............................180 29

V ANNEX V: COLLECTION OF INTERNET LINKS FOR THE USERS OF THE GUIDANCE30

...........................................................................................................181 31

VI ANNEX VI: BACKGROUND DOCUMENT TO THE GUIDANCE FOR SETTING 32

SPECIFIC CONCENTRATION LIMITS FOR SUBSTANCES CLASSIFIED FOR 33

REPRODUCTIVE TOXICITY ACCORDING TO REGULATION (EC) NO 1272/2008182 34

35

36

16



Tables 1

Table 2.12.1—a Examples of hazards, depending on the property of the emitted gas, when 2

substances and mixtures are in contact with water ................................ 121 3

Table 2.16.4—a Minimum mass loss of specimens after different exposure times 4

(corresponding to the criterion of 6.25 mm/year) .................................. 162 5

Table 2.16.4—b Minimum intrusion depths after exposure times (corresponding to the 6

criterion of localized corrosion of 6.25 mm/year) ................................... 162 7

Table 2.16.7—a Examples of classified and non classified substances and mixtures in Class 8

2.16 ................................................................................................. 167 9

10

No table of figures entries found. 11

Figures 12

Figure 2.4.4—a Decision logic for oxidising gases (Decision logic 2.4 of GHS) .................. 63 13

Figure 2.5.4—a Decision logic for gases under pressure (Decision logic 2.5 of GHS) ......... 68 14

Figure 2.6.4—a Amended GHS decision logic for flammable liquids to include derogations 15

for gas oil, diesel, light heating, sustained combustibility and for phrases 16

EUH018, EUH209 and EUH209A .......................................................... 76 17

Figure 2.7.4—a Decision logic for flammable solids (Decision logic 2.7 of GHS) ................ 83 18

Figure 2.8.4—a Decision logic 2.8 for self-reactive substances and mixtures .................... 93 19

Figure 2.8.7—a Decision logic for self-reactive substance example: NP, technically pure ... 98 20

Figure 2.9.4—a Decision logic for pyrophoric liquids (Decision logic 2.9 of GHS) ............... 102 21

Figure 2.10.4—a Decision logic for pyrophoric solids (Decision logic 2.10 of GHS) .............. 109 22

Figure 2.11.4—a Extrapolation towards large volumes .................................................... 117 23

Figure 2.11.7—a Volume dependency of the critical temperature for charcoal .................... 120 24

Figure 2.12.4—a Decision logic for substances and mixtures which, in contact with water, 25

emit flammable gases (Decision logic 2.12 of GHS) ................................ 126 26

Figure 2.13.4—a Decision logic for oxidising liquids (Decision logic 2.13 of GHS) ............... 135 27

Figure 2.14.4—a Decision logic for oxidising solids (Decision logic 2.14 of GHS) ................ 143 28

Figure 2.15.4—a Decision logic 2.15 for organic peroxides .............................................. 152 29

Figure 2.16.1—a Potential pH (also called Pourbaix) diagram for iron in water at 25 °C, 30

indicating stable form of the Fe element and implicitly, corrosion domains 159 31

Figure 2.16.4—a Example of testing equipment available on the market to perform UN Test 32

C.1 .................................................................................................. 164 33

Figure 2.16.4—b Decision logic for substances and mixtures corrosive to metals (Decision 34

logic 2.16 of GHS) ............................................................................. 165 35

Figure 2.16.7—a Example of corroded metal plates after testing according to UN Test C.1 36

for a classified mixture ....................................................................... 167 37

38

No table of figures entries found. 39



List of Abbreviations 1

2

1. PART 1: GENERAL PRINCIPLES FOR CLASSIFICATION AND 3

LABELLING 4

5

[See separate document for the text of Part 1 under consultation] 6

7

1.1. INTRODUCTION 8

1.2. THE SIGNIFICANCE OF THE TERMS ‘FORM OR PHYSICAL STATE’ 9

AND ‘REASONABLY EXPECTED USE’ WITH RESPECT TO 10

CLASSIFICATION ACCORDING TO CLP 11

12

1.3. SPECIFIC CASES REQUIRING FURTHER EVALUATION – LACK OF 13

BIOAVAILABILITY 14

1.4. USE OF SUBSTANCE CATEGORISATION (READ ACROSS AND 15

GROUPING) AND (Q)SARS FOR CLASSIFICATION AND LABELLING 16

1.5. SPECIFIC CONCENTRATION LIMITS AND M-FACTORS 17

1.6. MIXTURES 18

19

1.7. THE APPLICATION OF ANNEX VII 20

1.7.1. 21

22

23

24

25

26

27

28

29

30

31

32

33

18



1

2. PART 2: PHYSICAL HAZARDS 2

2.0. INTRODUCTION 3

2.0.1 General remarks about the prerequisites of classification and testing 4

The purpose of this chapter is to give some general guidance with respect to the classification of 5

physical hazards, the generation of test data and their interpretation. The intention of CLP is to 6

identify hazards of chemical substances and mixtures and to provide a systematic approach – 7

using classification - to communicate them based on harmonized criteria. The classification 8

process involves three steps: 9

1. gathering of relevant information regarding the hazards of a substance or mixture 10

(Articles 5 – 8 of CLP); 11

2. evaluation of hazard information to ascertain the hazards associated with the substance 12

or mixture (Article 9 of CLP); and 13

3. a decision on whether the substance or mixture will be classified as a hazardous 14

substance or mixture and the degree of hazard, where appropriate, by comparison of the 15

data with agreed hazard classification criteria (Article 13 of CLP). 16

Generally for both, substances and mixtures, the tests required in Annex I of CLP must be 17

performed, unless there is adequate and reliable information already available. Testing is 18

required to determine physical hazards including the physico-chemical properties necessary for 19

the respective classification unless alternative methods are specifically permitted. Before 20

undertaking testing of the substance or mixture, enquiries should be made to ascertain the 21

availability of data, e.g. flash points, on the substance or mixture. 22

2.0.2 Safety 23

In most cases, the classification is based on test data which are determined in a laboratory. 24

Special care is required when new or unknown substances or mixtures are tested. If possible, 25

preliminary tests should be carried out before larger quantities are handled. Appendix 6 of the 26

UN Recommendations on the transport of dangerous goods Manual of Tests and Criteria (UN-27

MTC) 'Screening procedures' allows gathering valuable information about physico-chemical 28

properties based on small-scale tests. Further aspects of safety are given in the general 29

introduction, Section 1.4 of the UN-MTC or within the individual test procedures. 30

2.0.3 General conditions for testing 31

Samples offered for testing must in all aspects be representative of the substance or mixture to 32

be classified. Therefore, it is helpful to characterise or specify the sample for the purposes of 33

documentation (i.e. batch number, production code, impurities etc.). Further characterisation 34

(i.e. analysis) is highly recommended in cases where the presence of diluents, activators, 35

stabilisers or moisture may influence the outcome of the test. 36

In some cases, additional parameters (e.g. physical condition, particle size (including 37

nanomaterials) (see Chapter 1.2) and shape (form), specific surface area, density, crystal 38

structure) may influence the test result. The tests must be performed on the substance or 39

mixture in the appropriate physical form where changes in that form may influence the outcome 40

of the test (see also Articles 5 and 6 of CLP and Chapter 1.2 in this guidance on form and 41

physical state). 42



2.0.4 Physical state 1

The physical state determines which hazard classes should be considered for testing. As the CLP 2

states1, hazard classification is based on intrinsic properties of the substance or mixture which 3

are determined not only by its physical state but also its form. 4

As mentioned in the Chapter 1.2 of this guidance the same solid substance or mixture may have 5

different forms such as flakes, pills, or powder. Furthermore, e.g. a powder may contain 6

particles of different size, and particles of the same size may have different shapes, crystallinity 7

or allotropy etc. These differences may result in different intrinsic properties, and consequently, 8

different physical hazards of the powder. Therefore not only the physical appearance, but also 9

other parameters should be considered when identifying the form, since it may trigger different 10

classifications of the same substance or mixture. 11

An example of different classification due to different intrinsic properties of forms is red 12

phosphorus (flammable solid) and white phosphorus (phyrophoric solid) (different allotropes). It 13

is therefore important to evaluate case by case whether available information on the physical 14

properties of the substance and mixture placed on the market, is applicable to the examined 15

form, and whether additional testing should be performed. 16

If further testing is required, the choice of the test method should be done after thorough 17

evaluation of its suitability for the substance or mixture, as the properties of the form (e.g. for 18

powders especially size and shape of the particle) may have a significant effect on the test 19

results. 20

The definitions for gases, liquids and solids are given in Annex I, Part 1 of CLP: 21

Annex I: Part 1, 1.0. Definitions

Gas means a substance which:

(i) at 50 °C has a vapour pressure greater than 300 kPa (absolute); or

(ii) is completely gaseous at 20 °C at a standard pressure of 101.3 kPa;

Liquid means a substance or mixture which:

(i) at 50 °C has a vapour pressure of not more than 300 kPa (3 bar);

(ii) is not completely gaseous at 20 °C and at a standard pressure of 101,3 kPa; and

(iii) which has a melting point or initial melting point of 20 °C or less at a standard

pressure of 101,3 kPa;

Solid means a substance or mixture which does not meet the definitions of liquid or gas.

In some cases (i.e. viscous substances or mixtures), a specific melting point cannot be 22

determined. Such a substance or mixture must be regarded as a liquid if either the result of the 23

ASTM D 4359-90 test as amended (standard test method for determining whether a material is 24

a liquid or a solid) indicates ‘liquid’ or the result of the test for determining fluidity 25

(penetrometer test) prescribed in Section 2.3.4 of Annex A of ADR indicates ‘not pasty’. 26

2.0.5 Quality 27

The determination of data must be based on the methods named in Annex I, Part 2 of CLP. For 28

most hazard classes in Annex I, Part 2 of CLP there is reference made to the UN-MTC which 29

gives very detailed descriptions of the test methods. For the classification of flammable gases, 30

oxidising gases and for the determination of the flash point there are references to international 31

1 CLP Article 5(1), 6(1) and 8(6).

20



standards in Annex I, Part 2 of CLP. Whenever possible, the laboratory should validate the 1

performance of the methods used e.g. by participating in inter-laboratory testing or by using 2

reference materials. Any deviation from the test procedure or standard should be documented 3

and, if necessary, justified. 4

The reliability of all test results used for the classification of hazardous substances and mixtures 5

is important and therefore their transparency and comparability must be ensured. 6

For these purposes, CLP requires in Article 8 the following: 7

Article 8 (5)

[…]

Where new tests for physical hazards are carried out for the purposes of this Regulation,

they shall be carried out, at the latest from 1 January 2014, in compliance with a relevant

recognised quality system or by laboratories complying with a relevant recognised standard.

[…]

It is highly recommended to follow this already before 1 January 2014. In general, the following 8

alternative strategies can be pursued: 9

1. compliance with the principles of good laboratory practice (GLP) (as formerly required by 10

the DSD); 11

2. application of EN ISO/IEC 17025 General requirements for the competence of testing 12

and calibration laboratories as amended as a relevant recognised standard; 13

3. other internationally recognised standards of comparable scope. 14

Any laboratory that carries out physical hazard tests for classification purposes can therefore 15

choose how to fulfil the quality requirements of CLP. 16

2.1. EXPLOSIVES 17

2.1.1. Introduction 18

The requirements in Chapter 2.1 ‘Explosives’ of Annex I of CLP are identical to those in Chapter 19

2.1 of GHS2. 20

The classification of explosives according to the GHS is almost entirely adopted based on the UN 21

Recommendations on the Transport of Dangerous Goods – Model Regulations (UN RTDG Model 22

Regulations), which are appropriate for transport and also storage of packaged explosives. 23

The classification of substances, mixtures and articles in the class of explosives and further 24

allocation to a division is a very complex procedure. References to Part I of the UN-MTC and 25

related expertise are necessary. 26

2.1.2. Definitions and general considerations for the classification of 27

explosives 28

The following definition is given in CLP for the class of explosives. 29

Annex I: 2.1.1.1. The class of explosives comprises

2 Globally Harmonised System of Classification and Labelling of Chemicals (GHS), Fifth revised edition, United Nations, 2013.



(a) explosive substances and mixtures;

(b) explosive articles, except devices containing explosive substances or mixtures in such

quantity or of such a character that their inadvertent or accidental ignition or initiation

shall not cause any effect external to the device either by projection, fire, smoke, heat

or loud noise; and

(c) substances, mixtures and articles not mentioned in points (a) and (b) which are

manufactured with a view to producing a practical, explosive or pyrotechnic effect.

Additional remark related to the applicability of 2.1.1.1 (a) (see also UN RTDG Model 1

Regulations, 2.1.1.1 (a)): 2

a substance or mixture which is not itself an explosive but which can form an explosive 3

atmosphere of gas, vapour or dust is not included in this class; 4

a substance or mixture with explosive properties, but where the predominant hazard is 5

covered by another class (e.g. organic peroxides, self-reactive substances and 6

mixtures), is not included in the class of explosives. 7

In addition the following definitions apply for explosives: 8

Certain physical hazards (due to explosive properties) are altered by dilution, as is the case for 9

desensitized explosives, by inclusion in a mixture or article, packaging or other factors. 10

Explosive substances and mixtures wetted with water or alcohols, or diluted with other 11

substances to suppress their explosive properties, may be treated differently to their non-12

wetted or non-diluted counterparts i.e. different hazard classes may apply, depending on the 13

physical properties of the wetted/diluted substance or mixture. 14

2.1.3. Relation to other physical hazards 15

For safety reasons, substances, mixtures or articles which have already been classified as 16

Explosives (Class 1 according to the UN RTDG Model Regulations) should not be considered for 17

classification in any other physical hazard classes. Since the explosion hazard is more severe 18

than other physical hazards there is no need to further perform classification tests for other 19

potential physical hazards. 20

Annex I: 2.1.1.2.

[…]

An explosive substance or mixture is a solid or liquid substance or mixture of substances

which is in itself capable by chemical reaction of producing gas at such a temperature and

pressure and at such a speed as to cause damage to the surroundings. Pyrotechnic

substances are included even when they do not evolve gases.

A pyrotechnic substance or mixture is a substance or mixture of substances designed to

produce an effect by heat, light, sound, gas or smoke or a combination of these as the result

of non-detonative self-sustaining exothermic chemical reactions.

An unstable explosive is an explosive which is thermally unstable and/or too sensitive for

normal handling, transport and use.

An explosive article is an article containing one or more explosive substances or mixtures.

A pyrotechnic article is an article containing one or more pyrotechnic substances or mixtures.

An intentional explosive is a substance, mixture or article which is manufactured with a view

to produce a practical explosive or pyrotechnic effect.

22



When considering substances and mixtures for classification within the hazard class explosives, 1

the following checks should be performed with respect to other hazard classes: 2

Substances, mixtures and articles that have been manufactured with a view to producing a 3

practical explosive or pyrotechnic effect, are classified as explosives by definition according to 4

2.1.1.1(c) of Annex I of the CLP. It should be checked whether such a substance or mixture is 5

an unstable explosive. 6

Thermally unstable substances or mixtures that are not classified as explosives should be 7

considered for classification as self-reactive substances and mixtures. 8

Mixtures of oxidising substances and mixtures with combustible material that are not classified 9

as explosives should be considered for classification as self-reactive substances and mixtures, 10

oxidising liquids or oxidising solids. 11

Due to the complexity of these issues, expert advice should always be sought when dealing with 12

classification of substances and mixtures with potentially explosive properties. 13

2.1.4. Classification of substances, mixtures or articles as explosives 14

2.1.4.1. Identification of hazard information 15

Information on the following types of hazards is relevant for the evaluation of substances, 16

mixtures and articles for the class of explosives: 17

sensitivity to shock; 18

effects of heating and ignition under confinement; 19

thermal stability; 20

sensitiveness to impact and friction; 21

mass explosion hazard; 22

projection hazard; 23

fire and radiant heat hazard. 24

2.1.4.2. Screening procedures and waiving of testing 25

The screening procedure is described in: 26

CLP, Annex I, Part 2, paragraphs 2.1.4.2 and 2.1.4.3; Appendix 6 of the UN-MTC. 27

The screening procedure may be used for new substances or mixtures which are suspected of 28

having explosive properties. It should not be used for substances and mixtures manufactured 29

with the intention of producing a practical explosive or pyrotechnic effect. 30

Explosive properties are associated with the presence of certain chemical groups in a molecule 31

which can react to produce very rapid increases in temperature and/or pressure. The screening 32

procedure is aimed at identifying the presence of such reactive groups and the potential for 33

rapid energy release. 34

Examples of groups which may indicate explosive properties are: 35

C-C unsaturation (e.g. acetylenes, acetylides, 1, 2-dienes); 36

C-Metal, N-Metal (e.g. Grignard reagents, organo-lithium compounds); 37

Contiguous nitrogen atoms (e.g. azides, aliphatic azo compounds, diazonium salts, 38

hydrazines, sulphonylhydrazides); 39

Contiguous oxygen atoms (e.g. peroxides, ozonides); 40

N-O (e.g. hydroxyl amines, nitrates, nitro compounds, nitroso compounds, N-oxides, 41

1,2-oxazoles); 42

N-halogen (e.g. chloramines, fluoroamines); 43

O-halogen (e.g. chlorates, perchlorates, iodosyl compounds). 44



A substance or mixture is not classified as explosive: 1

a. when there are no chemical groups associated with explosive properties present in the 2

molecule; 3

or 4

b. when the substance or mixture contains chemical groups associated with explosive 5

properties which include oxygen and the calculated oxygen balance is less than -200; 6

The oxygen balance is calculated for the chemical reaction: 7

OOHC 2zyx 2

z

4

yx

OHCO 22 2

yx

8

Using the formula: 9

Oxygen balance = weightmolecular

z2yx21600

10

or 11

c. when the organic substance or a homogenous mixture of organic substances contains 12

chemical groups associated with explosive properties but the exothermic decomposition 13

energy is less than 500 J/g and the onset of exothermic decomposition is below 500 ºC. 14

(The temperature limit is to prevent the procedure being applied to a large number of 15

organic materials which are not explosive but which will decompose slowly above 500 ºC 16

to release more than 500 J/g.) The exothermic decomposition energy may be 17

determined using a suitable calorimetric technique; 18

or 19

d. for mixtures of inorganic oxidising substances with organic material(s), the concentration 20

of the inorganic oxidising substance is: 21

less than 15 % by mass, if the oxidising substance is assigned to Categories 1 or 2; 22

less than 30 % by mass, if the oxidising substance is assigned to Category 3. 23

If the screening procedure identifies the substance or mixture to be a potential explosive or if it 24

is a mixture containing any known explosives, the classification (acceptance) procedure for the 25

class of explosives (see Section 2.1.4.5.1) has to be applied. If the exothermic decomposition 26

energy of organic materials is less than 800 J/g, a UN gap test is not required, neither according 27

to Series 1 Type (a) nor according to Series 2 Type (a). 28

2.1.4.3. Classification criteria 29

The criteria for the classification of explosives are given in the following tables. 30

Annex I: 2.1.2.1. Substances, mixtures and articles of this class are classified as an unstable

explosive on the basis of the flowchart in Figure 2.1.2. The test methods are described in

Part I of the UN RTDG, Manual of Tests and Criteria.

2.1.2.2. Substances, mixtures and articles of this class, which are not classified as an

unstable explosive, shall be assigned to one of the following six divisions depending on the

type of hazard they present:

(a) Division 1.1 Substances, mixtures and articles which have a mass explosion hazard

(a mass explosion is one which affects almost the entire quantity present virtually

instantaneously);

24



(b) Division 1.2 Substances, mixtures and articles which have a projection hazard but

not a mass explosion hazard;

(c) Division 1.3 Substances, mixtures and articles which have a fire hazard and either a

minor blast hazard or a minor projection hazard or both, but not a mass explosion

hazard:

(i) combustion of which gives rise to considerable radiant heat; or

(ii) which burn one after another, producing minor blast or projection effects or

both;

(d) Division 1.4 Substances, mixtures and articles which present no significant hazard:

substances, mixtures and articles which present only a small hazard in the event of

ignition or initiation. The effects are largely confined to the package and no projection

of fragments of appreciable size or range is to be expected. An external fire shall not

cause virtually instantaneous explosion of almost the entire contents of the package;

(e) Division 1.5 Very insensitive substances or mixtures which have a mass explosion

hazard:

substances and mixtures which have a mass explosion hazard but are so insensitive

that there is very little probability of initiation or of transition from burning to

detonation under normal conditions;

(f) Division 1.6 Extremely insensitive articles which do not have a mass explosion

hazard:

articles which contain only extremely insensitive substances or mixtures and which

demonstrate a negligible probability of accidental initiation or propagation.

2.1.2.3. Explosives, which are not classified as an unstable explosive, shall be classified in

one of the six divisions referred to in section 2.1.2.2 based on Test Series 2 to 8 in Part I of

the UN RTDG, Manual of Tests and Criteria according to the results of the tests laid down in

Table 2.1.1:

Table 2.1.1

Criteria for explosives

Category Criteria

Unstable explosives or

explosives of Divisions 1.1

to 1.6

For explosives of Divisions 1.1 to 1.6, the following are the core

set of tests that need to be performed:

Explosibility: according to UN Test Series 2 (section 12 of the UN

RTDG, Manual of Tests and Criteria). Intentional explosives (¹)

shall not be subject to UN Test Series 2.

Sensitiveness: according to UN Test Series 3 (section 13 of the

UN RTDG, Manual of Tests and Criteria).

Thermal stability: according to UN Test 3(c) (sub-section 13.6.1

of the UN RTDG, Manual of Tests and Criteria).

Further tests are necessary to allocate the correct Division.

(¹) This comprises substances, mixtures and articles which are manufactured with a view to

producing a practical, explosive or pyrotechnic effect.



Where the test is conducted in the package form and the packaging is changed, a further test 1

must be conducted where it is considered that the change in packaging will affect the outcome 2

of the test. 3

Classification tests must be performed on the substance or mixture as supplied. If the same 4

chemical is to be presented in a physical form different from that which was tested and which is 5

considered likely to materially alter its performance in a classification test, the substance or 6

mixture must also be tested in the new form. 7

2.1.4.4. Testing and evaluation of hazard information 8

Where test data are available, these must be evaluated against the set criteria for classification. 9

When the screening procedure indicates that a substance or mixture may possess explosive 10

properties, a cautious approach when performing the tests is necessary to ensure safe handling. 11

For information on the test procedures see the following Section 2.1.4.5 where the individual 12

test series are described in context with the respective decision logic. 13

The test procedures for the classification of explosives are described in detail in the Part I of the 14

UN-MTC. 15

2.1.4.5. Classification procedure and decision logics 16

Any substance, mixture or article having or suspected of having explosives characteristics must 17

be considered for classification in the hazard class of explosives. Substances, mixtures and 18

articles classified in this hazard class must be assigned to the appropriate division or must be 19

classified as unstable explosive. 20

The classification is divided into two stages, the acceptance procedure and the assignment 21

procedure. 22

In the acceptance procedure, intrinsic explosive properties of a substance, mixture or article are 23

determined through tests of its sensitivity, stability and explosion effects. If the substance, 24

mixture or article is not characterised as unstable explosive and is provisionally accepted into 25

the class of explosives, it is then necessary to ascertain the correct division by the assignment 26

procedure. The further subdivision into compatibility groups A to S is described in detail in the 27

UN RTDG Model Regulations, Section 2.1.2. The compatibility groups and their recommended 28

combination identify types of explosives which are deemed to be compatible, e.g. for combined 29

storage or transportation and can therefore be used to distinguish technical requirements 30

(especially) in these sectors. However, assignment of compatibility groups is not part of the 31

classification system according to CLP. 32

The tests for acceptance and the further tests to determine the correct division are grouped into 33

eight test series. Classification procedures, test methods and criteria are described in detail in 34

Part I of the UN-MTC. 35

NOTE: The person responsible for the classification of explosives should be experienced in

this field and be familiar with the criteria for classification.

36

26



Annex I: Figure 2.1.2

Procedure for provisional acceptance of a substance, mixture or article in the class

of explosives (Class 1 for transport)



2.1.4.5.1. Acceptance procedure 1

The acceptance procedure is used to determine whether or not a substance, mixture or article is 2

a candidate for the class of explosives or is an unstable explosive. 3

The test methods used for deciding on provisional acceptance into the class of explosives are 4

grouped into four series, numbered 1 to 4 (see CLP Annex I, Figure 2.1.2). 5

The numbering of Test Series 1 to 4 relates to the sequence of assessing the results rather than 6

the order in which the tests should be conducted. It may be important for the safety of test 7

personnel that certain tests, using small amounts of material, be conducted first 8

before proceeding to experiment with larger quantities. 9

Starting the testing procedure with Test Series 3 is highly recommended, because these tests 10

involve relatively small sample sizes, which reduces the risk to test personnel. 11

Test Series 1 12

Within Test Series 1 the question ‘Is it an explosive substance / mixture?’ is answered on the 13

basis of the results of three types of tests to assess possible explosive effects. The question is 14

answered ‘Yes’ if a ‘+’ is obtained in any of the three types of tests. If the answer is ‘No’, the 15

substance / mixture is rejected from this class; it is not an explosive. Under certain conditions 16

the test Type 1 (a) can be replaced by certain tests of Test Series F, see UN-MTC, Section 17

11.3.5. 18

The three types of test used are (recommended test is indicated within brackets): 19

Type 1 (a): a shock test with defined booster and confinement to determine the ability 20

of the substance to propagate a detonation (UN Gap test); 21

Type 1 (b): a test to determine the effect of heating under confinement (Koenen test); 22

and 23

Type 1 (c): a test to determine the effect of ignition under confinement (time/pressure 24

test). 25

Test Series 2 26

Series 2 tests are used to answer the question ‘Is the substance / mixture too insensitive for 27

acceptance into this Class?’. In general, the basic apparatus and method used is the same as 28

that for Test Series 1 but with less stringent criteria, e.g. in the case of gap tests, the gap used 29

is greater than zero. The question is answered ‘No’ if a ‘+’ is obtained in any of the three types 30

of test. If the answer is ‘Yes’, the substance / mixture is rejected from this class; it is not an 31

explosive. Under certain conditions the test Type 2 (a) can be replaced by certain tests of Test 32

Series F, see UN-MTC, Section 12.3.4. 33

The following three types of test are used (recommended test is indicated within brackets): 34

Type 2 (a): a shock test with defined initiation system and confinement to determine 35

sensitivity to shock (UN gap test); 36

Type 2 (b): a test to determine the effect of heating under confinement (Koenen test); 37

and 38

Type 2 (c): a test to determine the effect of ignition under confinement (Time/pressure 39

test). 40

If the substance or mixture is manufactured with a view to produce a practical explosive or 41

pyrotechnic effect, it is unnecessary to conduct Test Series 1 and 2 for purposes of 42

classification. 43

28



Test Series 3 1

As stated above it is recommended to carry out Test Series 3 before Test Series 1 and 2 for 2

safety reasons due to the small sample amount needed. It is also recommended to carry out 3

Test Series 3 even if negative results have been obtained in Test Series 1 and/or 2 because only 4

Test Series 3 gives information about the thermal stability and the sensitivity to mechanical 5

stimuli (impact and friction). 6

Test Series 3 is used to answer the questions ‘Is the substance / mixture thermally stable?’ and 7

‘Is the substance / mixture too dangerous in the form in which it was tested?’ This involves 8

tests for determining the sensitiveness of the substance or mixture to mechanical stimuli 9

(impact and friction), and to heat and flame. 10

The following four types of tests are used (recommended test is indicated within brackets): 11

Type 3 (a): a falling weight test to determine sensitiveness to impact (BAM 12

Fallhammer); 13

Type 3 (b): a friction; or impacted friction test to determine sensitiveness to friction 14

(BAM friction apparatus); 15

Type 3 (c): an elevated temperature test to determine thermal stability (thermal 16

stability test at 75 °C); and 17

Type 3 (d): an ignition test to determine the response of a substance or mixture to fire 18

(small scale burning test). 19

The first question is answered ‘No’ if a ‘+’ is obtained in Test type 3(c). Then the substance / 20

mixture is considered as thermally unstable and either classified as an unstable explosive or as 21

a self-reactive substance or mixture. 22

The second question is answered ‘Yes’ if a ‘+’ is obtained in any of the Test types 3(a), 3(b) or 23

3(d). If a ‘+’ is obtained, the substance / mixture may be encapsulated or packaged to reduce 24

its sensitiveness to external stimuli or is classified as an unstable explosive. Furthermore, the 25

explosive may be desensitized in order to suppress/reduce its explosive properties in which case 26

the classification procedure has to be restarted. 27

Test Series 4 28

Series 4 tests are intended to answer the question ‘Is the article, packaged article or packaged 29

substance or mixture too dangerous?’. Conditions which may occur during supply and use 30

include high /low temperature and high relative humidity, vibration, bumping and dropping. 31

The two types of test to be carried out are: 32

Type 4 (a): a test of thermal stability for articles; and 33

Type 4 (b): a test to determine the hazard from dropping. 34

The question is answered ‘Yes’ if a ‘+’ is obtained in either Test type 4 (a) or 4 (b) and the 35

substance or mixture or article is classified as an unstable explosive. 36

It is important to note that a substance / mixture which fails Test Series 2 (i.e. it is sensitive 37

enough for acceptance into the class of explosives) may still, if properly packaged, leave the 38

class of explosives provided that it is not designed to have an explosive effect and does not 39

exhibit any explosive hazard in Test Series 6 of the assignment procedure (see example for 40

musk xylene). Such an exclusion from the class of explosives is restricted to the specific type 41

and size of package tested. 42

Especially for substances / mixtures, which have explosive properties according to Test Series 1 43

and/or 2 but can leave the class of explosives after Test Series 6 due to proper packaging, it is 44

necessary to communicate these properties in the Safety Data Sheet (SDS). Furthermore, the 45

results from Test types 3 (a) and 3 (b) should be documented in the SDS when they meet the 46



criteria of EU test method A.14 in Regulation (EC) No 440/2008 (these are substances with a 1

sensitiveness to impact, determined by UN Test Series 3 (a) (ii) of 40 J or less and/or a 2

sensitiveness to friction, determined by Test Series 3 (b) (i) of 360 N or less). 3

2.1.4.5.2. Assignment procedure to a division 4

The assignment procedure to one of six divisions, depending on the type of hazard they 5

present, applies to all substances, mixtures and/or articles that are candidates for class of 6

explosives. A substance, mixture or article must be assigned to the division which corresponds 7

to the results of the tests to which the substance, mixture or article, as offered for supply and 8

use, has been subjected. Other test results, and data assembled from accidents which have 9

occurred, may also be taken into account. 10

The test methods used for assignment to a division are grouped into three series – numbered 5 11

to 7 – designed to provide the information necessary to answer the questions in Figure 2.1.3 in 12

CLP. 13

NOTE: The person responsible for the classification of explosives should be experienced in

this field and be familiar with the criteria for classification.

14

30




Procedure for assignment to a division in the class of explosives (Class 1 for

transport)

1



Test Series 5 1

Test Series 5 is only carried out for explosive substances/mixtures which are very insensitive 2

and therefore candidates for division 1.5. Typical substances/mixtures are blasting agents such 3

as ANFO, slurries, and emulsion explosives. 4

The results from three types of series 5 tests are used to answer the question ‘Is it a very 5

insensitive explosive substance / mixture with a mass explosion hazard?’. 6

The test types are (recommended test is indicated within brackets): 7

Type 5 (a): a shock test to determine the sensitivity to intense mechanical stimulus 8

(cap sensitivity test); 9

Type 5 (b): thermal tests to determine the tendency of transition from deflagration to 10

detonation (French or USA DDT test); and 11

Type 5 (c): a test to determine if a substance, when in large quantities, explodes when 12

subjected to a large fire. 13

The question is answered ‘No’ if a ‘+’ is obtained in any of the three test types. A candidate for 14

Division 1.5 should pass one test of each type. 15

Test Series 6 16

The results from four types of series 6 tests are used to determine which division, amongst 17

Divisions 1.1, 1.2, 1.3 and 1.4, corresponds most closely to the behaviour of the substance, 18

mixture or article to be classified if a load is involved in a fire resulting from internal or external 19

sources or an explosion from internal sources. The results are also necessary to assess whether 20

a substance, mixture or article can be assigned to Compatibility Group S of Division 1.4 and 21

whether or not it should be excluded from this class. Test Series 6 should be applied to 22

packages of substances, mixtures or articles in the condition and form in which they are offered 23

for supply and use. 24

The four test types are (recommended test is indicated within brackets): 25

Type 6 (a): a test on a single package to determine if there is mass explosion of the 26

contents (single package test); 27

Type 6 (b): a test on packages of an explosive substance, mixture or explosive 28

articles, or non-packaged explosive articles, to determine whether an 29

explosion is propagated from one package to another or from a non-30

packaged article to another (stack test); and 31

Type 6 (c): a test on packages of an explosive substance, mixture or explosive 32

articles, or non-packaged explosive articles, to determine whether there is 33

a mass explosion or a hazard from dangerous projections, radiant heat 34

and/or violent burning or any other dangerous effect when involved in a 35

fire (bonfire test); 36

Type 6 (d): a test on an unconfined package of explosive articles to which special 37

provision 347 of Chapter 3.3 of the UN RTDG Model Regulations applies, to 38

determine if there are hazardous effects outside the package arising from 39

accidental ignition or initiation of the contents. 40

Test types 6 (a), 6 (b), 6 (c) and 6 (d) are performed in alphabetical order. However, it is not 41

always necessary to conduct tests of all types. Test type 6 (a) may be waived if explosive 42

articles are carried without packaging or when the package contains only one article. Test type 43

6 (b) may be waived if in each type 6 (a) test: 44

32



the exterior of the package is undamaged by internal detonation and/or ignition; or 1

the contents of the package fail to explode, or explode as feebly as would exclude 2

propagation of the explosive effect from one package to another in test type 6(b). 3

Test type 6(c) may be waived if, in a type 6(b) test, there is practically instantaneous explosion 4

of virtually the total contents of the stack. In such cases the product is assigned to Division 1.1. 5

Test type 6 (d) is a test used to determine whether a 1.4S classification is appropriate and is 6

only used if Special Provision 347 of Chapter 3.3 of the UN RTDG Model Regulations applies. The 7

results of test series 6 (c) and 6 (d) indicate if 1.4S is appropriate, otherwise the classification is 8

1.4 other than S. 9

If a substance or mixture gives a ‘—‘ result (no propagation of detonation) in the Series 1 type 10

(a) test, the 6(a) test with a detonator may be waived. 11

If a substance gives a ‘—‘ result (no or slow deflagration) in a Series 2 type (c) test, the 6 (a) 12

test with an igniter may be waived. 13

Test Series 7 14

Test Series 7 aims at military explosives (Extremely Insensitive Substance: EIS or article 15

containing an EIS) and is generally not relevant for explosives for civil use. Therefore the 16

individual tests are not described here. If needed, they can be found in the UN- MTC, Part I, 17

Section 17. 18

Test Series 8 19

The question whether a candidate for ammonium nitrate emulsion or suspension or gel, 20

intermediate for blasting explosives (ANE) is insensitive enough for classification as oxidising is 21

answered by series 8 tests. The three test types are (recommended test is indicated within 22

brackets): 23

Type 8 (a): a test to determine the thermal stability (Thermal Stability Test for ANE); 24

Type 8 (b): a shock test to determine sensitivity to intense shock (ANE gap test); and 25

Type 8 (c): a test to determine the effect of heating under confinement (Koenen test). 26

Test Series 8 is used to establish whether an ammonium nitrate emulsion or suspension or gel, 27

intermediate for blasting explosives (ANE) may leave the class of explosives or not. Substances 28

or mixtures failing any of the tests must be classified as explosives (Division 1.1. or 1.5) or as 29

an unstable explosive in accordance with CLP Annex I, Figure 2.1.4. If they pass all three tests 30

they are classified as an oxidising liquid or solid. 31

32




Procedure for the classification of ammonium nitrate emulsion, suspension or gel

(ANE)

1

34



2.1.5. Hazard communication for explosives 1

2.1.5.1. Pictograms, signal words, hazard statements and precautionary 2

statements 3

4

Annex I: Table 2.1.2

Label elements for explosives

Classificati

on

Unstable

Explosive

Division

1.1

Division

1.2

Division

1.3

Division

1.4

Division

1.5

Division

1.6

GHS

Pictograms

Signal Word

Danger Danger Danger Danger Warning Danger No signal word

Hazard Statement

H200: Unstable Explosive

H201: Explosive; mass

explosion hazard

H202: Explosive; severe

projection hazard

H203: Explosive; fire, blast

or projection hazard

H204: Fire or projection

hazard

H205: May mass explode in

fire

No hazard statement

Pre-cautionary Statement

Prevention

P201

P250

P280

P210

P230

P234

P240

P250

P280

P210

P230

P234

P240

P250

P280

P210

P234

P240

P250

P280

P210

P240

P250

P280

P210

P230

P234

P240

P250

P280

No pre-cautionary statement

Pre-cautionary

Statement

Response

P370+P372+P380

+P373

P370+ P372+P380

+P373

P370+ P372+P380

+P373

P370+ P372+P380

+P373

P370+ P372+P380

+P373

P370+P380+P375

P370+ P372+P380

+P373

No pre-cautionary

statement


Storage

P401 P401 P401 P401 P401 P401 No pre-cautionary statement


Disposal

P501 P501 P501 P501 P501 P501 No pre-cautionary statement

The wording of the Precautionary Statements is found in CLP Annex IV, Part 2. 5



The intrinsic explosive properties of substances and mixtures regarding their stability and 1

sensitivity are only investigated within Test Series 1, 2 and 3 during the acceptance procedure. 2

Subsequent tests for the assignment to the Divisions 1.1, 1.2, 1.3 and 1.4 (Test Series 6) are 3

carried out with the packaged substances, mixtures or articles. The type of packaging may 4

significantly influence the test outcome. 5

Consequently, there are some deficiencies in the hazard communication of the GHS for 6

unpacked or repacked explosive substances and mixtures, especially for substances and 7

mixtures, which are provisionally accepted in the class of explosives but are later rejected from 8

this class due to their packaging in the assignment procedure (see CLP Annex I, Figure 2.1.1 9

and Figure 2.1.3 and Section 2.1.4.5.1 of this guidance). These substances and mixtures have 10

explosive properties but there might be no hazard communication about these properties due to 11

the subsequent classification in a hazard class other than the class of explosives. Musk xylene is 12

an example which illustrates this issue (see Section 2.1.7.2). The results of Test Series 6 for 13

musk xylene in the specified packaging lead to the exclusion of this substance from the hazard 14

class of explosives. But musk xylene on its own (unpacked) shows explosive properties due to 15

heating under confinement (Koenen test). Also repacking of the substance in a packaging other 16

than the tested one can result in a completely different outcome of Test Series 6. 17

This issue is not sufficiently clarified under GHS, but should be kept in mind by everyone 18

applying the CLP criteria. 19

2.1.5.2. Additional labelling provisions 20

Explosives are normally classified in their transport packaging. The packaging itself may be 21

crucial for the classification. This is clear from the Figure 2.1.3 in Section 2.1.4.5.2 especially 22

when it comes to Test Series 6. The assignment of an explosive substance or mixture to a 23

particular Division within the hazard class of explosives is thus only valid for the substance and 24

mixture in the transport packaging in which it was tested. Because of the package-dependence 25

of the classification, paragraph 2.1.2.4 of the Annex I to the CLP prescribes: 26

Annex I: 2.1.2.4. If explosives are unpackaged or repacked in packaging other than the

original or similar packaging, they shall be retested.

Further, according to NOTE 1 to Table 2.1.2 in Section 2.1.3 of Annex I to CLP, unpackaged 27

explosives or explosives repacked in packaging other than the original or similar packaging 28

must have the following label elements: 29

Annex I: 2.1.3. Hazard communication

[…]

NOTE 1: Unpackaged explosives or explosives repackaged in packaging other than the

original or similar packaging shall include the following label elements:

(a) the pictogram: exploding bomb;

(b) the signal word: “Danger”; and

(c) the hazard statement: 'explosive; mass explosion hazard'

unless the hazard is shown to correspond to one of the hazard categories in Table 2.1.2, in

which case the corresponding symbol, signal word and/or the hazard statement shall be

assigned.

Normally, if explosives are unpackaged or repacked in packaging other than the original or 30

similar packaging the classification procedure needs to be performed again in order to 31

determine which Division the explosive belongs to in the new packaging. The label elements 32

36



prescribed in the NOTE 1 to Table 2.1.2, as quoted above, are the same as those of Division 1.1 1

and in practice this Division constitutes the most severe classification of a repackaged explosive. 2

(Please note that Table 2.1.2 foresees also the hazard category ‘Unstable explosive’, which is 3

assigned on the basis of the intrinsic properties of a substance or mixture via Test Series 3 and 4

it is not package dependent). Therefore, the CLP allows labelling of a repackaged explosive with 5

labelling corresponding to Division 1.1 instead of retesting. This, however, overestimates the 6

hazardous properties unless the explosive in fact belongs to Division 1.1. 7

Many explosives are supplied in inner packages which are placed together in an outer package 8

and where the entity as a whole, i.e. the combination of inner and outer packages, constitutes 9

the transport packaging. According to the UN RTDG Model Regulations and the modal transport 10

regulations (ADR, RID, ADN and IMDG Code, ICAO TI) the classification tests are performed in 11

the transport packaging. Under Article 33(1) of the CLP where the hazard pictograms(s) 12

required by CLP relate to the same hazard as in the rules for the transport of dangerous goods, 13

the respective CLP hazard pictogram(s) do not need to appear on the outer packaging. 14

The classification in accordance with rules on the transport of dangerous goods is almost 15

entirely identical to the corresponding classification procedure used in the CLP and hence the 16

CLP classification will automatically be known for the transport packaging. However, the CLP 17

classification for the inner package alone strictly speaking is not known to manufacturer, 18

importer or downstream user as this will not have been attained through the classification of the 19

transport packaging. On the other hand, it is normally not practicable to perform the required 20

tests on the inner packages. Therefore, normally the same classification as for the transport 21

packaging may be assumed for the inner packages. The labelling requirements for the inner 22

packages are the ones foreseen in Table 2.1.2 of Annex I to the CLP. However, the following 23

exceptions apply: 24

Transport packages in which the packaging is designed such that mass explosion is 25

prevented by the packaging, e.g. by arranging the individual inner packages crosswise 26

(so that they are not neighbouring each other) and by separating them with specified 27

material. This is especially the case when packing instruction P101 according to the 28

section 4.1.5 of the ADR applies. In this case the inner package should be labelled in 29

accordance with the Note 1 to Table 2.1.2 of Annex I to the CLP (i.e. as Division 1.1 30

unless tested otherwise). 31

Packages in which explosives of different divisions are contained (for such cases see 32

especially the mixed packing provisions MP 20 to MP 24 in section 4.1.10 of the ADR). 33

Furthermore, it does not apply if the packaging is changed, as stated in the Note 1 to 34

Table 2.1.2 of Annex I to the CLP. 35

Some R-phrases under DSD were not covered by hazard classes in the GHS. They are included 36

as supplemental hazard statements in Part 1 of Annex II to of CLP. The following EU hazard 37

statements are important in connection with explosive properties: 38

Annex II: 1.1.1. EUH001 – ‘Explosive when dry’

For explosive substances and mixtures as referred to in chapter 2.1 of part 2 of Annex I,

placed on the market wetted with water or alcohols or diluted with other substances to

suppress their explosives properties.

EUH001 must be assigned to explosives which are wetted, diluted, dissolved or suspended with 39

a phlegmatizer in order to reduce or suppress their explosive properties (desensitized explosives 40

in the sense of the foreseen new hazard class for desensitized explosives) and which do not 41

meet the criteria of the hazard class of explosives. 42

43



Annex II: 1.1.6. EUH044 – ‘Risk of explosion if heated under confinement’

For substances and mixtures not in themselves classified as explosive in accordance with

section 2.1 of part 2 of Annex I, but which may nevertheless display explosive properties in

practice if heated under sufficient confinement. In particular, substances which decompose

explosively if heated in a steel drum do not show this effect if heated in less-strong

containers.

Some substances and mixtures which may react explosively if heated under confinement are 1

not covered adequately by the classification system. This may e.g. be the case for: 2

substances or mixtures which are exempted from the class of explosives based on their 3

packaging and according to results of the Test Series 6; 4

substances or mixtures with a SADT of more than 75 °C for a 50 kg package which 5

therefore cannot be classified as self-reactive. 6

EUH044 must be assigned to such substances or mixtures, in order to make the user aware 7

about these properties. 8

2.1.5.3. Further communication requirements 9

According to Note 2 to Table 2.1.2, explosive properties of certain substances and mixtures 10

which are exempted from classification as explosives must be communicated to the user via the 11

SDS (when one is required). 12


[…]

NOTE 2: Substances and mixtures, as supplied, with a positive result in Test Series 2 in Part

I, Section 12, of the UN RTDG, Manual of Tests and Criteria, which are exempted from

classification as explosives (based on a negative result in Test Series 6 in Part I, Section 16

of the UN RTDG, Manual of Tests and Criteria,) still have explosive properties. The user shall

be informed of these intrinsic explosive properties because they have to be considered for

handling – especially if the substance or mixture is removed from its packaging or is

repackaged – and for storage. For this reason, the explosive properties of the substance or

mixture shall be communicated in Section 2 (Hazards identification) and Section 9 (Physical

and chemical properties) of the Safety Data Sheet and other sections of the Safety Data

Sheet, as appropriate

2.1.6. Relation to transport classification 13

Division 1.1 – 1.6 within Class 1 of the UN RTDG Model Regulations covers explosive 14

substances, mixtures and articles. Normally, classification included in the UN RTDG Model 15

Regulations and the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) can 16

be used one-to-one when deriving the CLP classification for explosives, which are packaged in 17

authorised transport packaging. See Annex VII for additional information on transport 18

classification in relation to CLP classification. 19

For the use of other packaging or for unpacked substances and mixtures the additional labelling 20

provisions (see Section 2.1.5.2) have to be observed or re-testing is necessary. 21

2.1.7. Examples of classification for explosives 22

Examples are given below for the classification of substances; however, equivalent information 23

would be needed for mixtures. 24

38



2.1.7.1. Example of substances and mixtures fulfilling the classification 1

criteria 2

a. RESULTS FROM APPLICATION OF THE ACCEPTANCE PROCEDURE 3

Step Test Conclusion Rationale

0. General data:

0.1 Name of the substance / mixture: Hexanitrostilbene

1. Is the substance / mixture a candidate for ammonium nitrate

emulsion, suspension or gel,

intermediate for blasting explosive (ANE)?

No

2. Is the substance / mixutre manufactured with the view to producing a practical explosive or pyrotechnic effect?

Yes

3. Test Series 3

3.1 Thermal stability: 75 °C / 48 hour test (test 3(c))

Result: ‘—‘, thermally stable

3.2 Impact sensitivity: BAM Fallhammer test (test 3(a)(ii))

Result: Limiting impact energy 5 J

‘—‘, not too dangerous in form tested

3.3 Friction sensitivity: BAM friction test (test 3(b)(i))

Result: Limiting load > 240 N

‘—‘, not too dangerous in form tested

4. Is the substance / mixture thermally stable?

Yes

5. Is the substance / mixture too dangerous in the form in which it was tested?

No

6. Conclusion: PROVISIONALLY ACCEPT INTO THIS CLASS

10.1 Exit: Apply the

assignment procedure

b. RESULTS FROM APPLICATION OF THE ASSIGNMENT PROCEDURE 4




1. Is the substance a candidate for Division 1.5?

No

Result: Package the substance

2. Test Series 6

2.1 Effect of initiation in the

package:

Test 6(a) with detonator Result: detonation,

crater

2.2 Effect of propagation: Type 6(b) with detonator Result: detonation of the whole stack of packages, crater

2.4 Effect of fire engulfment: Test 6(c) may be waived because of the result of 6(b) test.

3. Is the result a mass explosion? Yes

4. Conclusion: Assignment to Division 1.1

2.1.7.2. Example of substances and mixtures not fulfilling the 1

classification criteria 2

This example is taken from the UN-MTC, Part I, Section 10.5.2, Figure 10.5. 3

a. RESULTS FROM APPLICATION OF THE ACCEPTANCE PROCEDURE 4


0. General data:

0.1 Name of the substance / mixture: 5-tert-butyl-2,4,6-trinitro-m-xylene (musk

xylene)

1. Is the substance / mixutre a candidate for ammonium nitrate emulsion, suspension or gel, intermediate for blasting explosive ANE?

No

2. Is the substance / mixture

manufactured with the view to producing a practical explosive or pyrotechnic effect?

No

3. Test Series 1

3.1 Propagation of Detonation: UN gap test (test 1(a))

Result:’+’, propagation of detonation

40




3.2 Effect of heating under confinement:

Koenen test (test 1(b))

Result: Limiting diameter 12.0 mm

Fragmentation type ‘F’ ‘+’, shows some explosive effects on heating under

confinement

3.3 Effect of ignition under confinement:

Time/pressure test (test 1(c)(i))

Result: ‘—’, no effect on ignition under confinement

4. Is it an explosive substance /

mixutre?

Yes

5. Test Series 2

5.1 Sensitivity to shock: UN gap test (test 2(a))

Result: ‘—’, not sensitive to shock

5.2 Effect of heating under confinement:

Koenen test (test 2(b))

Result: Limiting diameter 12.0 mm

Fragmentation type ‘F’ ‘+’, violent effect on heating under

confinement.

5.3 Effect of ignition under confinement:

Time/pressure test (test 2(c)(i))

Result: ‘—’, no effect on ignition under confinement

6. Is the substance / mixture too insensitive for acceptance into this class?

No

Conclusion: Substance to be considered for this class

7. Test Series 3

7.1 Thermal stability: 75 °C/48 hour test (test 3(c))

Result: ‘—’, thermally stable

7.2 Impact sensitivity: BAM Fallhammer test

(test 3(a)(ii))

Result: Limiting impact energy 25 J", not too

dangerous in form tested.

7.3 Friction sensitivity: BAM friction test (test 3(b)(i))

Result: Limiting load > 360 N

‘—’, not too dangerous in form tested

8. Is the substance / mixture

thermally stable?

Yes




9. Is the substance / mixture too dangerous in the form in which it was tested?

No

10. Conclusion: PROVISIONALLY ACCEPT INTO THIS

CLASS

10.1 Exit Apply the assignment procedure

1

42



b. RESULTS FROM APPLICATION OF THE ASSIGNMENT PROCEDURE 1


1. Is the substance a candidate for Division 1.5?

No

Result: Package the substance

2. Test Series 6

2.1 Effect of initiation in the package:

Test 6(a) with detonator

Result: Only localised decomposition around detonator

No significant reaction

2.2 Effect of ignition in the package:

Test 6(a) with igniter

Result: Only localised decomposition around igniter

No significant reaction

2.3 Effect of propagation: Type 6(b) test

not required as no effect outside package between packages in 6(a) test

2.4 Effect of fire engulfment: Test 6 Result: Only slow

burning with black smoke occurred.

No effects which

would hinder fire fighting

3. Is the result a mass explosion? No

4. Is the major hazard that from dangerous projections?

No

5. Is the major hazard radiant heat and/or violent burning but with no

dangerous blast or projection hazard?

No

6. Is there nevertheless a small hazard in the event of ignition or initiation?

No

7. Is the substance manufactured with the view to producing a practical explosive or pyrotechnic effect?

No

8. Conclusion: NOT AN EXPLOSIVE

8.1 Exit Consider for another class (e.g. flammable solid)

2



2.2. FLAMMABLE GASES (INCLUDING CHEMICALLY UNSTABLE GASES) 1


The criteria for ‘Flammable gases (including chemically unstable gases)’ are found in Annex I, 3

Section 2.2 of CLP and are identical to those in Chapter 2.2 of GHS3. 4


flammable gases (including chemically unstable gases) 6

Annex I: 2.2.1. Definitions

2.2.1 Flammable gas means a gas or gas mixture having a flammable range with air at 20

°C and a standard pressure of 101.3 kPa.

2.2.1.2. A chemically unstable gas means a flammable gas that is able to explode even in

the absence of air or oxygen.

The flammable range of a flammable gas is defined between the ‘lower flammability limit’ (LFL) 7

in air and the ‘upper flammability limit’ (UFL) in air. In technical literature, the terms ‘lower 8

explosion limit’ (LEL) and ‘upper explosion limit’ (UEL) are often used instead of the LFL and 9

UFL, respectively. 10

The hazard class of flammable gases also covers chemically unstable gases as defined above. 11


Annex I: 2.2.2. Classification criteria

[…]

Note: Aerosols shall not be classified as flammable gases; see section 2.3.

For flammable gases that are packaged in aerosol dispensers see 2.3 Aerosols. If classified as 13

aerosols, they do not have to be classified as flammable gases in addition. 14

2.2.4. Classification of substances and mixtures as flammable gases 15

(including chemically unstable gases) 16


Many gases are classified as flammable gases in Annex VI of CLP and more gases are classified 18

as flammable gases in the UN RTDG Model Regulations. 19

For gases that are not classified as flammable gases in Annex VI of CLP nor in the UN RTDG 20

Model Regulations, there is ample scientific literature giving the flammability range for most 21

gases (e.g. IEC 60079-20-1, Explosive atmospheres – Part 20-1: Material characteristics for gas 22

and vapour classification – Test methods and data as amended). 23

In the case a gas or gas mixture needs to be tested for flammability, a recognised international 24

standard must be used such as the EN 1839, Determination of explosion limits of gases and 25

vapours as amended or ISO 10156, Gases and gas mixtures – Determination of fire potential 26

and oxidising ability for the selection of cylinder valves outlets as amended. 27

3 GHS, Fifth revised edition, United Nations, 2013.

44



Information on a number of chemically unstable gases can be found in the UN-MTC, Section 35. 1

Tables 35.1 and 35.2 within UN-MTC, Section 35.3.2.1 contain information on a number of 2

chemically unstable gases together with their classification and Category. 3

If information on other gases than the ones mentioned in the above tables is needed a test 4

method for determination of chemical instability of gases and gas mixtures is described in UN-5

MTC, Section 35. However, it should be noted that this test method is not applicable to liquefied 6

gas mixtures. In case the gaseous phase above a liquefied gas mixture may become chemically 7

unstable after withdrawal, this should be communicated via the SDS. 8

2.2.4.2. Screening procedures and waiving of testing for gas mixtures 9

There are thousands of gas mixtures on the market and there are a limited number of test 10

reports for the flammability of gas mixtures in the scientific literature. Tests to determine the 11

flammability range are time consuming and expensive for gas mixtures which are often 12

prepared on demand. In most of the cases, the formulator of the gas mixture will use a 13

calculation method as described in ISO 10156 as amended (see Section 2.2.4.4) to determine if 14

the mixture is flammable or not. 15

If the calculations in accordance with ISO 10156 as amended show that a gas mixture is not 16

flammable it is also not classified as chemically unstable and therefore it is not necessary to 17

carry out the tests for determining chemical instability for classification purposes. 18

Expert judgement should be applied to decide whether a flammable gas or gas mixture is a 19

candidate for classification as chemically unstable in order to avoid unnecessary testing of gases 20

where there is no doubt that they are stable. Functional groups indicating chemical instability in 21

gases are triple bonds, adjacent or conjugated double-bonds, halogenated double-bonds and 22

strained rings. 23

Gas mixtures containing only one chemically unstable gas are not considered as chemically 24

unstable and therefore do not have to be tested for classification purposes if the concentration 25

of the chemically unstable gas is below the higher of the following generic concentration limits: 26

a. the lower explosion limit (LEL) of the chemically unstable gas; or 27

b. 3 mole%. 28

Furthermore, for some gases there are also specific concentration limits available and these are 29

indicated in the tables 35.1 and 35.2 within UN-MTC, Section 35.3.2.1. 30


The criteria for the classification of flammable gases (including chemically unstable gases) are 32

given in the following tables: 33

34




ISO 10156 as amended describes a test method and a calculation method for the classification 2

of flammable gases. The test method may be used in all cases, but must be used when the 3

calculation method cannot be applied. 4

The calculation method applies to gas mixtures and can be applied when the TCi for all 5

flammable components and the Kk for all inert components are available. These are listed for a 6

number for gases in ISO 10156 as amended. In the absence of TCi value for a flammable gas, 7

the value of the LFL can be used and ISO 10156 proposes the value of 1.5 where no Kk value is 8

listed. The calculation method described in ISO 10156 as amended uses the criterion that a gas 9

mixture is considered non-flammable in air if: 10

11

Equation 2.2.4.4.a 1

'

1

n

i ic

i

T

A 12

where: 13

Equation 2.2.4.4.b

p

k

kk

n

i

i

i

i

BKA

AA

11

' 14

and where: 15

Annex I: 2.2.2. Table 2.2.1

Criteria for flammable gases

Category Criteria

1

Gases, which at 20 °C and a standard pressure of 101.3 kPa:

(a) are ignitable when in a mixture of 13 % or less by volume in air; or

(b) have a flammable range with air of at least 12 percentage points regardless of

the lower flammable limit.

2 Gases, other than those of Category 1, which, at 20 °C and a standard pressure of

101.3 kPa, have a flammable range while mixed in air.

Annex I: 2.2.2 Table 2.2.2

Criteria for chemically unstable gases

Category Criteria

A Flammable gases which are chemically unstable at 20 °C and a pressure of 101.3

kPa.

B Flammable gases which are chemically unstable at a temperature greater than 20

°C and/or a pressure greater than 101.3 kPa.

46



iA' is the equivalent content of the i:th flammable gas in the mixture, in % 1

ciT is the maximum content of flammable gas i which, when mixed with nitrogen, 2

is not flammable in air, in % 3

iA is the molar fraction of the i:th flammable gas in the mixture, in % 4

kB is the molar fraction of the k:th inert gas in the mixture, in % 5

kK is the coefficient of equivalency of the inert gas k relative to nitrogen 6

n is the number of flammable gases in the mixture 7

p is the number of inert gases in the mixture 8

The principle of the calculation method is the following: 9

Where a gas mixture contains an inert diluent other than nitrogen, the volume of this diluent is 10

adjusted to the equivalent volume of nitrogen using the equivalency coefficient for the inert gas11

kK . From this the equivalent contents iA' are then derived through Equation 2.2.4.4.b, which 12

should be viewed as the corresponding concentration of the flammable gases if nitrogen was the 13

only inert gas present in the mixture. In Equation 2.2.4.4.a the equivalent contents are then 14 compared to the constants

ciT , which have been experimentally found using nitrogen as the 15

(only) inert gas. 16

It should be noted that ISO 10156 uses molar fractions in some of its equations. For most gases 17

under normal (i.e. non-extreme) conditions, however, the volume fraction can be assumed to 18

be equal to the molar fraction, which is the same as assuming ideal gas behaviour for all gases 19

in the mixture. Furthermore, although normally a fraction is a number ranging from 0 to 1, in 20

this case it is easier to express it as percentage, i.e. the fraction multiplied by 100. 21

The calculation method described in ISO 10156 as amended determines only if the mixture is 22

flammable or not. It does not determine a flammability range and therefore the calculation 23

method cannot determine if the mixture is flammable Category 1 or Category 2. Therefore, to 24

be on the safe side, mixtures determined to be flammable according the calculation method are 25

classified Flammable gas; Category 1. If, however, there is a need to distinguish between 26

Category 1 and Category 2, the lower and the upper explosion limits have to be determined by 27

using a suitable test method (e.g. EN 1839 or ISO 10156 as amended). 28

For mixtures containing both flammable and oxidising components, special calculation methods 29

are described in ISO 10156 as amended. 30

Gases or compressed gas mixtures that are classified as flammable have to be considered for 31

classification as chemically unstable in addition. If the screening procedures described in Section 32

2.2.4.2 are not conclusive, the gas or gas mixture has to be tested. The test method is 33

described in UN-MTC, Section 35. It uses the same equipment as the test method for oxidising 34

gases according to ISO 10156 as amended and therefore could be applied by laboratories that 35

also carry out the tests for oxidising gases. 36

2.2.4.5. Decision logic 37

Classification of flammable gases is laid down in the following flow-charts which are applicable 38

according to CLP. 39

NOTE: The person responsible for the classification of flammable gases (including

chemically unstable gases) should be experienced in this field and be familiar with the

criteria for classification.



2.2.4.5.1. Decision logic for flammable gases 1


Flammable gases

2

Gaseous substance or mixture of gases

Does it have a flammable range with air at

20 °C and a standard pressure of 101.3 kPa?

At 20 °C and a standard pressure of 101.3

kPa, does it:

a. ignite when in a mixture of 13 % or

less by volume in air?; or

b. have a flammable range with air of at

least 12 percentage points regardless

of the lower flammable limit?

YES

NO

NO

YES

Not classified

Category 1

Danger

Category 2

No pictogram

Warning

48



2.2.4.5.2. Decision logic for chemically unstable gases 1


Chemically unstable gases

2

Flammable gas or gas mixture

Is it chemically unstable at 20 °C and a

standard pressure of 101.3 kPa?

Is it chemically unstable at a temperature

greater than 20 °C and/or a pressure greater than 101.3 kPa?

NO

NO

YES

YES

Category A

(chemically

unstable gas)

No additional

pictogram

No additional

signal word

Category B

(chemically

unstable gas)

No additional

pictogram

No additional

signal word

Not classified as chemically unstable



2.2.5. Hazard communication for flammable gases (including chemically 1

unstable gases) 2


statements 4


Label elements for flammable gases (including chemically unstable gases)

Classification

Flammable gas Chemically unstable gas

Category 1 Category 2 Category A Category B

GHS Pictogram

No pictogram No additional

pictogram

No additional

pictogram

Signal Word Danger Warning No additional

signal word

No additional

signal word

Hazard

Statement

H220: Extremely

flammable gas

H221: Flammable

gas

Additional hazard

statement H230:

May react

explosively even

in the absence of

air

Additional hazard

statement H231:

May react

explosively even

in the absence of

air at elevated

pressure and/or

temperature

Precautionary

Statement

Prevention

P210 P210 P202 P202

Precautionary

Statement

Response

P377

P381

P377

P381

Precautionary

Statement

Storage

P403 P403

Precautionary

Statement

Disposal


50




The criteria for flammable gases Category 1 correspond to the criteria that are in use for 2

classifying flammable gases in the UN RTDG Model Regulations. Consequently all gases listed as 3

flammable in the UN RTDG Model Regulations and in the modal transport regulations (ADR, RID, 4

ADN and IMDG Code, ICAO TI) must be classified as Flam.Gas 1; H220. See Annex VII for 5

additional information on transport classification in relation to CLP classification. 6

2.2.7. Example of classification for flammable gases 7

Example mixture: 2 % (H2) + 6 % (CH4) + 27 % (Ar) + 65 % (He)

Calculation steps:

Step 1: Assign the gases and state their molar fractions, assuming the molar fractions are

equal to the volume fractions (ideal gas behaviour for all gases).

H2 is flammable gas 1, yielding 1A = 2 mole %

CH4 is flammable gas 2, yielding 2A = 6 mole %

Ar is inert gas 1, yielding 1B = 27 mole %

He is inert gas 2, yielding 2B = 65 mole %

n=2 since there are two flammable gases in the mixture

p =2 since there are two inert gases in the mixture

Step 2: Look up the values of ciT and

kK in ISO 10156 as amended.

1cT = 5.5 mole %

2cT = 8.7 mole %

1K = 0.55

2K = 0.9

Step 3: Calculate the equivalent gas contentsiA' for the flammable gases according to

Equation 2.2.4.4.b

659.02755.062

2'1

A = 2.46 mole %

659.02755.062

6'2

A = 7.38 mole %

Step 4: Calculate the flammability of the gas mixture according to Equation 2.2.4.4.a



7.8

38.7

5.5

46.2'''

2

2

1

12

1

cci ci

i

T

A

T

A

T

A= 1.29

Step 5: Compare the outcome to the criterion in Equation 2.2.4.4.a

Since 1.29 > 1, this particular gas mixture is considered to be flammable.

1

2

52



2.3. AEROSOLS 1


Identical criteria related to the flammability of aerosols are found in Annex I, Section 2.3 of CLP, 3

Chapter 2.3 of GHS4 as well as in the Aerosol Dispensers Directive (ADD) 75/324/EEC5. 4


aerosols 6

Annex I: 2.3.1. Aerosols, this means aerosol dispensers, are any non-refillable receptacles

made of metal, glass or plastics and containing a gas compressed, liquefied or dissolved under

pressure, with or without a liquid, paste or powder, and fitted with a release device allowing

the contents to be ejected as solid or liquid particles in suspension in a gas, as a foam, paste

or powder or in a liquid state or in a gaseous state.


There is no direct relation to other physical hazards. 8

1. Annex I, 2.3.2.1.

[…]

Note 2:

Aerosols do not fall additionally within the scope of Sections 2.2 (flammable gases), 2.5

(gases under pressure), 2.6 (flammable liquids) and 2.7 (flammable solids). Depending on

their contents, aerosols may however fall within the scope of other hazard classes, including

their labelling elements.


5 Directive as last amended by Commission Directive 2013/10/EU [ OJ L 77, 20.03.2013, p.20].



2.3.4. Classification of aerosols 1


Annex I: 2.3.2.1. Aerosols shall be classified in one the three categories of this hazard class,

depending on their flammable properties and their heat of combustion. They shall be

considered for classification in Category 1 or 2 if they contain more than 1% components (by

mass) which are classified as flammable according to the following criteria set out in this Part:

– Flammable gases (see section 2.2);

– Liquids with a flash point ≤ 93 °C, which includes Flammable Liquids according to section

2.6;

– Flammable solids (see section 2.7);

Or their heat of combustion is at least 20kJ/g.

Note 1:

Flammable components do not cover pyrophoric, self-heating or water-reactive substances

and mixtures because such components are never used as aerosol contents.

[…]

2.3.2.2. An aerosol shall be classified in one of the three categories for this Class on the basis

of its components, of its chemical heat of combustion and, if applicable, of the results of the

foam test (for foam aerosols) and of the ignition distance test and enclosed space test (for

spray aerosols) in accordance with Figures 2.3.1(a) to 2.3.1(c) of this Annex and sub-sections

31.4, 31.5 and 31.6 of Part III of the UN RTDG, Manual of Tests and Criteria. Aerosols which

do not meet the criteria for inclusion in Category 1 or Category 2 shall be classified in

Category 3.

Note:

Aerosols containing more than 1% flammable components or with a heat of combustion of at

least 20 kJ/g, which are not submitted to the flammability classification procedures in this

section shall be classified as aerosols, Category 1.

Under the ADD and also in UN-MTC, Section 31, flammability classification for aerosols refers to 3

‘extremely flammable’, ‘flammable’ and ‘non-flammable’. This respectively corresponds to the 4

terms ‘Aerosol, Category 1’, ‘Aerosol, Category 2’ and ‘Aerosol, Category 3’ which are used in 5

CLP. 6

The following identical criteria can be found in both CLP and ADD: 7

The aerosol is classified as ‘Aerosol, Category 3’ if it contains 1 % or less flammable 8

components and the chemical heat of combustion is less than 20 kJ/g. 9

The aerosol is classified as ‘Aerosol, Category 1’ if it contains 85 % or more flammable 10

components and the chemical heat of combustion exceeds or is equal to 30 kJ/g. 11

All other aerosols should be submitted to the appropriate flammability classification procedures 12

in order to select the appropriate Category 1, 2 or 3. However, if these are not submitted to the 13

flammability classification procedures they must be automatically classified as ‘Aerosol, 14

Category 1’. 15

The chemical heat of combustion is determined in accordance with CLP Annex I, 2.3.4.1 which 16

is identical to point 1.10 of the Annex to ADD. 17

54




Results from the ignition distance test, the enclosed space test and the foam flammability test 2

may be used for the classification related to the flammability of aerosols. These test methods 3

are described under point 6.3 of the Annex to ADD and are therefore available in all EU 4

languages. They are also described in the UN-MTC Section 31. 5

After the evaluation according to the appropriate criteria (see previous sections) the aerosol is 6

classified in one of the three categories. 7


The classification procedure is also laid down in the following flow-charts which are applicable 9

according to CLP. 10

NOTE: The person responsible for the classification of aerosols should be experienced in this

field and be familiar with the criteria for classification.



2.3.4.3.1. Decision logic for aerosols 1

Annex I: Figure 2.3.1 (a)

for aerosols

AEROSOL

Does it contain ≤ 1% flammable

components (by mass) and does it have a

heat of combustion < 20 kJ/g?

Category 3

No pictogram

Warning

Does it contain ≥ 85% flammable

components (by mass) and does it have a

heat of combustion ≥ 30 kJ/g?

Category 1

Danger

For spray aerosols, go to decision logic

2.3.1(b)

For foam aerosols, go to decision logic

2.3.1(c)'

'

2

3

YES

NO

YES

NO

56



2.3.4.3.2. Decision logic for spray aerosols 1

Annex I: Figure 2.3.1 (b)

Spray aerosols

2

SPRAY AEROSOL

In the ignition distance test, does ignition occur at a distance ≥ 75 cm?

Does it have a heat of combustion < 20 kJ/g?

In the ignition distance test, does ignition occur at a distance ≥ 15 cm?

In the enclosed space ignition test; is:

(a) the time equivalent ≤ 300 s/m³or

(b) the deflagration density ≤ 300 g/m³?

YES

Category 3

No pictogram

Warning

Category 1

Danger

Category 2

Warning

Category 2

Warning

NO

NO

NO

Category 2

Warning

YES

NO

YES

YES



2.3.4.3.3. Decision logic for foam aerosols 1

Annex I: Figure 2.3.1 (c)

Foam aerosols

2

FOAM AEROSOL

In the foam test, is:

(a) the flame height ≥ 20 cm and the flame duration ≥ 2 s; or (b) the flame height ≥ 4 cm and the flame duration ≥ 7 s?

In the foam test; is the flame height ≥ 4 cm and the flame duration ≥ 2 s?

Category 3

No pictogram

Warning

Category 1

Danger

Category 2

Warning

NO

NO

YES

YES

58



2.3.5. Hazard communication for aerosols 1


statements 3


Label elements for aerosols

Classification Category 1 Category 2 Category 3

GHS Pictograms

No pictogram

Signal Word Danger Warning Warning

Hazard Statement

H222: Extremely

flammable aerosol

H229: Pressurised

container: May burst

if heated.

H223: Flammable

aerosol

H229: Pressurised


if heated.

H229: Pressurised


if heated.

Precautionary

Statement

Prevention

P210

P211

P251

P210

P211

P251

P210

P251

Precautionary

Statement Response

Precautionary

Statement Storage P410 + P412 P410 + P412

P410 + P412

Precautionary

Statement Disposal



The ADD imposes additional labelling requirements on all aerosols, flammable or not, including 6

those which are not within the scope of CLP. 7

For example: 8

Where an aerosol dispenser contains flammable components but is not classified as flammable 9

(i.e. ‘Aerosol, Category 3’), the quantity of flammable material contained in the aerosol 10

dispenser must be stated clearly on the label, in the form of the following legible and indelible 11

wording: ‘X % by mass of the contents are flammable’. 12




Aerosol dispensers (UN 1950) belong to Class 2 in the UN RTDG Model Regulations and in the 2

modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI). Flammability 3

classification criteria are harmonised between CLP and in the modal transport regulations (ADR, 4

RID, ADN and IMDG Code, ICAO TI). 5

Aerosols, Category 1 and 2 fall under Division 2.1 (sometimes referred to as Class 2.1 or Group 6

F). Aerosols, Category 3 fall under Division 2.2 (sometimes referred to as Class 2.2 or Group A 7

or O). Depending on their contents other classifications may be relevant. See Annex VII for 8


2.3.7. Examples of classification for aerosols 10

For reasons of simplification the active materials chosen in the examples have been considered 11

as non-combustible materials (Hc = 0 kJ/g). However this is not the case in practice. 12

2.3.7.1. Examples of aerosols fulfilling the classification criteria 13

Deodorant:

Composition:

Butane/propane: 70 % (flammable components, Hc = 43.5 kJ/g)

Ethanol: 25 % (flammable components, Hc = 24.7 kJ/g)

Others: 5 % (non-flammable components, Hc = 0 kJ/g)

This spray aerosol contains 95 % of flammable components, and its chemical heat of combustion

equals 36.6 kJ/g (= 0.70 * 43.5 + 0.25 * 24.7).

This aerosol is classified as Aerosol, Category 1.

Air freshener (wet):

Composition:



This spray aerosol contains 30 % of flammable components and its chemical heat of combustion equals 13.1 kJ/g.

In the ignition distance test, the ignition occurs at less than 75 cm but more than 15 cm.


Shaving foam:

Composition:



60



This foam aerosol contains 4 % of flammable components and its chemical heat of combustion equals 1.7 kJ/g.

In the foam test, the flame height is less than 4 cm and the flame duration less than 2 s.


However, according to the requirements of ADD, the quantity of flammable components must be stated clearly on the label: ‘4% by mass of the contents are flammable’.

2.3.7.2. Examples of aerosols not fulfilling the classification criteria 1

By definition, all aerosol dispensers fall under one of the three categories for this hazard class. 2

3



2.4. OXIDISING GASES 1


The requirements in Chapter 2.4 ‘Oxidising gases’ of Annex I of CLP are identical to those in 3

chapter 2.4 of the GHS6. 4


oxidising gases 6

Annex I: 2.4.1. Oxidising gas means any gas or gas mixture which may, generally by

providing oxygen, cause or contribute to the combustion of other material more than air

does.


Oxidising gases do not need to be classified in any other hazard class apart from ‘Gases under 8

pressure’ where appropriate. 9

2.4.4. Classification of substances and mixtures as oxidising gases 10


There are not many pure gases that are oxidising. Most oxidising gases are identified as such in 12

the UN RTDG Model Regulations and in ISO 10156 Gases and gas mixtures: Determination of 13

fire potential and oxidizing ability for the selection of cylinder valve outlets as amended. 14


There are thousands of gas mixtures containing oxidising gases on the market and there are 16

very few test reports on oxidising potential of gas mixtures in the scientific literature. Tests 17

according to ISO 10156 as amended in order to determine the oxidising potential are time 18

consuming and expensive for gas mixtures which are often prepared on demand. In most of the 19

cases, the formulator of the gas mixture will use a calculation method as described in ISO 20

10156 as amended. 21



Criteria for oxidising gases

Category Criteria

1 Any gas which may, generally by providing oxygen, cause or contribute to the

combustion of other material more than air does.

Note:

‘Gases which cause or contribute to the combustion of other material more than air does’

means pure gases or gas mixtures with an oxidising power greater than 23.5 % as

determined by a method specified in ISO 10156 as amended.


62



Please note that ISO 10156-2:2005 has been integrated into the revised version ISO 1

10156:2010. ISO 10156:2010 supersedes EN 720-2:1996 and ISO 10156-2:2005. 2


ISO 10156 as amended describes a test method and a calculation method for the classification 4

of oxidising gases. The test method may be used in all cases, but must be used when the 5

calculation method cannot be applied. 6

The calculation method applies to gas mixtures and can be applied only when the Ci for all 7

oxidising components and the Kk for all inert components are available. These are listed for a 8

number of gases in ISO 10156 as amended. For gas mixtures the calculation method described 9

in ISO 10156 as amended uses the criterion that a gas mixture should be considered as more 10

oxidising than air if the ‘Oxidising Power’ (OP) of the gas mixture is higher than 0.235 (23.5 %). 11

The OP is calculated as follows: 12

Equation 2.4.4.4.a

n

i

p

k

kki

n

i

ii

BKx

Cx

OP

1 1

1 13

Where: 14

xi is the molar fraction of the i:th oxidising gas in the mixture, in % 15

Ci is the coefficient of oxygen equivalency of the i:th oxidising gas in the mixture 16

Kk is the coefficient of equivalency of the inert gas k relative to nitrogen 17

Bk is the molar fraction of the k:th inert gas in the mixture, in % 18

n is the number of oxidising gases in the mixture 19

p is the number of inert gases in the mixture 20

For mixtures containing both flammable and oxidising components, special calculation methods 21

are described in ISO 10156 as amended. 22


Classification of oxidising gases is done according to decision logic 2.4.4.1 as included in the 24

GHS. 25

NOTE: The person responsible for the classification of oxidising gases should be

experienced in this field and be familiar with the criteria for classification.



Figure 2.4.4—a Decision logic for oxidising gases (Decision logic 2.4 of GHS) 1

2

3

2.4.5. Hazard communication for oxidising gases 4


statements 6


Label elements for oxidising gases

Classification Category 1

GHS Pictogram

Signal word Danger

Hazard statement H270: May cause or intensify fire; oxidiser

Precautionary Statement Prevention P220

P244

Precautionary Statement Response P370 + P376

Precautionary Statement Storage P403

Precautionary Statement Disposal



Most oxidising gases are classified as such with subsidiary risk 5.1 in the UN RTDG Model 9

Regulations. Consequently all gases listed as oxidising in the UN RTDG Model Regulations and in 10

the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) must be classified as 11

Ox. Gas 1. See Annex VII for additional information on transport classification in relation to CLP 12

classification. 13

Gaseous substance or mixture of gases

Does the gas contribute to the combustion of

other material more than air does?

Not classified

Category 1

Danger

YES

NO

64



2.4.7. Example of classification for oxidising gases 1

2.4.7.1. Example of substances and mixtures not fulfilling the 2


EXAMPLE OF A CLASSIFICATION USING THE CALCULATION METHOD OF ISO 10156 AS AMENDED

Example Mixture: 9 % (O2) + 16 % (N2O) + 75 % (N2)

Calculation steps

Step 1: Ascertain the coefficient of oxygen equivalency (Ci) for the oxidising gases in the mixture and

the nitrogen equivalency factors (Kk) for the non-flammable, non-oxidising gases.

Ci (N2O) = 0.6 (nitrous oxide)

Ci (O) = 1 (oxygen)

Kk (N2) = 1 (nitrogen)

Step 2: Calculate the Oxidising Power (OP) of the gas mixture according to Equation 2.4.4.4.a

186.0175.016.009.0

6.016.0109.0

1 1

1

n

i

p

k

kki

n

i

ii

BKx

Cx

OP

0.186 < 0.235 (18.6 % < 23.5 %), therefore the mixture is not considered as an

oxidising gas.

4



2.5. GASES UNDER PRESSURE 1


The requirements in Chapter 2.5 ‘Gases under pressure’ of Annex I of CLP are identical to those 3

in Chapter 2.5 of GHS7. The hazard class ‘Gases under pressure’ corresponds to Class 2 ‘Gases’ 4

in the UN RTDG Model Regulations. 5

2.5.2. Definitions and general considerations for the classification of gases 6

under pressure 7

2.5.2.1. Definition of ‘gas’ 8

Annex I: 1.0. Gas means a substance which (i) at 50 °C has a vapour pressure greater

than 300 kPa (absolute); or (ii) is completely gaseous at 20 °C at a standard pressure of

101.3 kPa;

This definition means that substances and mixtures are considered as gases when their boiling 9

point or initial boiling point (BP) is not higher than 20 °C. Substances and mixtures with a 10

boiling point or initial boiling point higher than 20 °C are liquids except those few that develop a 11

vapour pressure higher than 300 kPa at 50 °C; these substances and mixtures are considered 12

as gases because of the pressure hazard when packaged. 13

Hydrogen fluoride (HF) with a BP of 19.4 °C is a borderline line case that has always been 14

classified as a liquid. 15

2.5.2.2. Definition of gases under pressure 16

Annex I: 2.5.1.1. Gases under pressure are gases or gas mixtures which are contained in a

receptacle at a pressure of 200 kPa (gauge) or more at 20 °C, or which are liquefied or

liquefied and refrigerated.

They comprise compressed gases, liquefied gases, dissolved gases and refrigerated liquefied

gases.

This definition means in practice that compressed gases or dissolved gases that are packaged at 17

a pressure less than 200 kPa are not classified for this hazard. 18

Dissolved gases packaged at a pressure less than 200 kPa (gauge) are liquids and should be 19

classified as such if they have other hazardous properties, e.g. flammable liquids. 20

Also, liquids packaged under a layer of inert gas (e.g. nitrogen or helium) remain to be 21

classified as liquids and not as gases under pressure. 22


Gases under pressure may also need to be classified for the hazard classes flammable gases 24

and oxidising gases where relevant. 25


66



2.5.4. Classification of substances and mixtures as gases under pressure 1


Many gases are identified as such in the UN RTDG Model Regulations and many flammable 3

gases and some oxidising gases are identified as gases in Annex VI of CLP. The UN RTDG Model 4

Regulations identifies further if the gas can be packaged as a ‘compressed gas’, a ‘liquefied gas’, 5

a ‘refrigerated liquefied gas’ and a ‘dissolved gas’. To determine whether a substance is a gas in 6

case it is not listed in the UN RTDG Model Regulations and in case of doubt, the following 7

physical characteristics are necessary: 8

the boiling point; 9

the vapour pressure at 50 °C. 10

See also IR & CSA, Chapter R.7a: Endpoint specific guidance, Section R.7.1.3 (Boiling point), 11

R.7.1.5 (Vapour pressure). 12

For those substances that meet the definition of a gas (see Section 2.5.2), the critical 13

temperature is also necessary. For the classification of gas mixtures based on the pseudo-14

critical temperature see Section 2.5.4.3. 15

The references according to Section 2.6.8 provide good quality data on boiling points, vapour 16

pressure and the critical temperature of substances. 17



Criteria for gases under pressure

Group Criteria

Compressed

gas

A gas which when packaged under pressure is entirely gaseous at

- 50 °C; including all gases with a critical temperature - 50 °C.

Liquefied gas

A gas which, when packaged under pressure, is partially liquid at

temperatures above - 50 °C. A distinction is made between:

i) high pressure liquefied gas: a gas with a critical temperature between

- 50 °C and + 65 °C; and

ii) low pressure liquefied gas: a gas with a critical temperature above +

65 °C.

Refrigerated

liquefied gas

A gas which when packaged is made partially liquid because of its low

temperature.

Dissolved gas A gas which when packaged under pressure is dissolved in a liquid phase

solvent.

Note:

Aerosols shall not be classified as gases under pressure. See section 2.3.




The critical temperature of pure gases is well defined and can be found in technical literature, 2

e.g. EN 13096 Transportable gas cylinders — Conditions for filling gases into receptacles — 3

Single component gases as amended. 4

For gas mixtures, the classification is based on the ‘pseudo-critical temperature’ which can be 5

estimated as the mole weighted average of the components’ critical temperatures. 6

Pseudo-critical temperature =

n

i

Critii

x1

T 7

where xi is the molar concentration of component i and Ti

Crit is the critical temperature (in °C 8

or in K) of the component i. 9


Classification of gases under pressure is done according to decision logic 2.5.4.1 as included in 11

the GHS. 12

NOTE: The person responsible for the classification of gases under pressure should be


68



Figure 2.5.4—a Decision logic for gases under pressure (Decision logic 2.5 of GHS) 1

2

Dissolved gas

Warning

The substance or mixture is a gas

Is the gas contained in a receptacle at a pressure of 200 kPa (gauge) or more at 20 °C, or is the gas liquefied or liquefied and

refrigerated?

Is the gas dissolved in a liquid phase solvent?

Not classified as a gas under pressure

Is the gas partially liquid because of its low temperature?

Is the gas partially liquid at temperatures above – 50 °C?

Is its critical temperature above + 65 °C?

Refrigerated liquefied gas

Warning

(Low pressure) Liquefied gas

Warning

Is its critical temperature between – 50 °C + 65°C?

Is the gas entirely in gaseous state at – 50 °C?

(High pressure) Liquefied gas

Warning

Compressed gas

Warning

Yes

Yes

Yes

Yes

Yes

Yes

No

No

No

No

No

No



2.5.5. Hazard communication for gases under pressure 1


statements 3


Label elements for gases under pressure

Classification Compressed gas Liquefied gas Refrigerated

liquefied gas Dissolved gas

GHS Pictogram

Signal Word Warning Warning Warning Warning

Hazard

Statement

H280: Contains

gas under

pressure; may

explode if heated

H280: Contains

gas under

pressure; may

explode if heated

H281: Contains

refrigerated

gas; may cause

cryogenic burns

or injury

H280:

Contains gas

under

pressure;

may explode

if heated

Precautionary

Statements

Prevention

P282

Precautionary

Statements

Response

P336 + P315

Precautionary

Statements

Storage

P410 + P403 P410 + P403 P403 P410 + P403

Precautionary

Statements

Disposal

Note:

Pictogram GHS04 is not required for gases under pressure where pictogram GHS02 or

pictogram GHS06 appears.


70




Gases are listed in UN RTDG Model Regulations and in the transport regulations (ADR, RID, 2

ADN)8 with an indication of the physical state in their name for compressed gases (e.g. Argon, 3

compressed), for refrigerated liquefied gas (e.g. Oxygen, refrigerated liquid) and for dissolved 4

gas (e.g. Acetylene, dissolved). These indications of the physical state 5

can be used to identify the group of gases under pressure according to CLP. The gas 6

names without an indication of the physical state are ‘liquefied gases’ by default. See Annex VII 7

for additional information on transport classification in relation to CLP classification. 8

9

8 The classification code according to the ADR, Sections 2.2.2.1.2 and 2.2.2.1.3 are: 1. Compressed gas; 2. Liquefied gas; 3. Refrigerated liquefied gas; 4. Dissolved gas. A asphyxiant; O oxidizing; F flammable; T toxic; TF toxic, flammable; TC toxic, corrosive; TO toxic, oxidizing; TFC toxic, flammable, corrosive; TOC toxic, oxidizing, corrosive.



2.5.7. Examples of classification for gases under pressure 1

2.5.7.1. Examples of substances and mixtures fulfilling the classification 2

criteria 3

2.5.7.1.1. Example mixture: 9 % (O2) + 16 % (N2O) + 75 % (N2) 4

Example mixture: 9 % (O2) + 16 % (N2O) + 75 % (N2)

Calculation steps:

Step 1: Ascertain the critical temperatures in Kelvin for the gases in the mixture:

Oxygen (O2): TCrit = -118.4 °C (= 154.75 K)

Nitrous Oxide (N2O): TCrit = +36.4 °C (= 309.55 K)

Nitrogen (N2): TCrit = -147 °C (= 126.15 K)

Step 2: Calculate the pseudo-critical temperature:

0.09 154.75 K + 0.16 309.55 K + 0.75 126.15 K= 158.7 Kelvin = - 115.08 °C

The pseudo-critical temperature is lower than -50 °C, therefore the mixture is a ‘compressed gas’.

5

72



2.6. FLAMMABLE LIQUIDS 1


The criteria for ‘Flammable liquids’ are found in Annex I, Section 2.6 of CLP and are not 3

identical to those of GHS9 as the respective GHS Chapter 2.6 contains additional classification 4

criteria - Category 4 for flammable liquids. 5


flammable liquids 7

Annex I: 2.6.1. Flammable liquid means a liquid having a flash point of not more than 60 °C.

The flash point is the lowest temperature of the liquid, corrected to a barometric pressure of 8

101.3 kPa, at which application of a test flame causes the vapour of the liquid to ignite 9

momentarily and a flame to propagate across the surface of the liquid under the specified 10

conditions of test. This means, the lower explosion limit is exceeded at the flash point. 11


For flammable liquids that are packaged in aerosol dispensers, see Section 2.3 on Aerosols. If 13

classified as flammable aerosols, they must not be classified as flammable liquids in addition 14

(see Section 2.3). 15

2.6.4. Classification of substances and mixtures as flammable liquids 16


For the decision if a substance or mixture is a liquid see Section 2.0.4. 18

For the classification of a substance or mixture as a flammable liquid, data on the flash point 19

and on the boiling point (or the initial boiling point) are needed. For experimental determination 20

of the flash point information on the viscosity of the liquid is needed, in order to select a 21

suitable method. Furthermore, in order to make use of the derogation for classification in 22

Category 3 according to Annex I Section 2.6.4.5 of CLP (see Section 2.6.4.3), information on 23

sustained combustibility is necessary. 24

Experimentally determined data or data taken from reliable data sources are to be preferred 25

over calculated ones. See also IR & CSA, Chapter R.7a: Endpoint specific guidance, Section 26

R.7.1.3 (Boiling point), R.7.1.9 (Flash point). 27

The references in Section 2.6.8 provide good quality data on boiling points (all three references) 28

and flash point (first reference) of substances. 29

Special care is required when viscous substances or mixtures are tested or when halogenated 30

compounds are present (see Section 2.6.4.4.1). 31


2.6.4.2.1. Boiling point 33

Normally calculation methods based on increments give satisfying results for substances and 34

mixtures. With respect to the criterion for distinguishing between Category 1 and 2 (boiling 35

point of 35 °C) only that method with a mean absolute error lower than 5 °C could be 36

recommended for screening. 37




2.6.4.2.2. Flash point 1

Calculation should work for pure liquids, neglecting impurities, if the vapour pressure curve and 2

lower explosion limit are accurately known. For mixtures, calculation of the flash point is 3

sometimes not reliable and at this time, it is not possible to predict what the accuracy of a 4

calculated value is. Calculation can be used as a screening test for mixtures, and a flash point 5

need not be determined experimentally if the calculated value using the method cited in CLP 6

Annex I, 2.6.4.3 is 5 °C greater than the relevant classification criterion (23 °C and 60 °C, 7

respectively). However, the restrictions outlined in the CLP Annex I, 2.6.4.2 must be taken 8

account of. 9

Calculation based on structural similarity or properties is often only applicable to a narrowly 10

defined set of substances. For mixtures they are not yet applicable. 11

Therefore for both flash point and boiling point experimental determination is recommended. 12


A flammable liquid has to be classified in one of the 3 categories of this class. 14


Label elements for flammable liquids

Category Criteria

1 Flash point < 23 °C and initial boiling point ≤ 35 °C

2 Flash point < 23 °C and initial boiling point > 35 °C

3 Flash point ≥ 23 °C and ≤ 60 °C1

(1) For the purpose of this Regulation gas oils, diesel and light heating oils having a flash

point between > 55 °C and ≤ 75 °C may be regarded as Category 3.

Note:

Aerosols shall not be classified as flammable liquids; see section 2.3.

15

Annex I: 2.6.4.5. Liquids with a flash point of more than 35 °C and not more than 60 °C

need not be classified in Category 3 if negative results have been obtained in the sustained

combustibility test L.2, Part III, section 32 of the UN RTDG, Manual of Tests and Criteria.

Gas oils, diesel and light heating oils in the flash point range of 55 °C to 75 °C may be regarded 16

as a whole. The reason is that these hydrocarbon mixtures have varying flash points in that 17

range due to seasonal requirements (EN 590 Automotive fuels – Diesel- Requirements and Test 18

Methods as amended). If they are regarded as a whole for CLP they have to be regarded as 19

Category 3. This states however no preliminary decision with respect to downstream 20

Regulations and legislation. 21


The assignment to the respective hazard category will determine the technical means to be 23

taken to avoid dangerous events. In combination with other safety characteristics like explosion 24

limits or auto ignition temperature this can lead to clear restrictions in the conditions of use. 25

The relevant data are to be communicated via the CSR and SDS (see IR/CSA Part F: Chemical 26

74



Safety Report, Part G: Extending the SDS and Guidance on compilation of safety data sheets 1

respectively). 2

2.6.4.4.1. Testing 3

Suitable methods are listed in CLP Annex I, Table 2.6.3. 4

In case of substances with a high decomposition potential, a method using small amounts of 5

liquid (e.g. EN ISO 3679 Determination of flash point - Rapid equilibrium closed cup method as 6

amended) is recommended to reduce the amount of substance under test. 7

The method to be used has to be chosen taking into account the properties of the liquid 8

(viscosity, halogenated compounds present) and the scope of the standard. 9

For classification purposes it is recommended to use the mean of at least two test runs. One of 10

these runs may be automated. In case of a deviation between manual and automated 11

determination above the tolerance limits of the method, the lower value should be taken or the 12

determination should be repeated with manual observation. If the experimentally determined 13

flash point is found to be within ± 2 °C a threshold limit when using a non-equilibrium method, 14

it is recommended to repeat the determination with an equilibrium method. 15

If no flash point is found up to 60 °C and (partly) halogenated compounds are present or if 16

there is the possibility of loss of volatile flammable or non-flammable components (i.e. the 17

liquid is a candidate for the assignment of EUH018, EUH209 or EUH209A) or if in doubt, the 18

explosion limits should be determined in order to decide whether labelling with EUH018, 19

EUH209 or EUH209A is appropriate. Determination of explosion limits should be carried out 20

according to EN 1839 Determination of explosion limits of gases and vapours as amended or 21

ISO 10156 Gases and gas mixtures – Determination of fire potential and oxidising ability for the 22

selection of cylinder valves outlets as amended or EN 15794 Determination of explosion points 23

of flammable liquids as amended. 24

Substances 25

For non-halogenated substances, the flash point is usually found 80 °C to 130 °C below the 26

boiling point. Special care has to be taken when a sample contains impurities with a lower 27

boiling point than the main compound. Even if their concentration is below 0.5 %, especially if 28

their boiling point is substantially lower, they may have a strong effect on the test result. 29

Impurities with a higher boiling point will normally have no effect on the flash point. 30

Within the respective scope, every standard is applicable. 31

Mixtures 32

The flash point may be lower than the lowest flash point of the components and non-volatile 33

components may influence the flash point. 34

Equilibrium methods are advised if the boiling points of the components of the mixture cover a 35

wide range of temperatures or their concentrations are very different. They are also advised in 36

case of viscous mixtures (alternatively: test methods with low heating rates (1 °C per min) 37

using a stirrer). 38

In case of viscous mixtures or if an inerting substance is present at low concentrations and this 39

is a highly volatile compound, the ignitability of the mixture may depend on the temperature at 40

which the tests are started. When an inerting substance is present temperature ranges may 41

exist where the vapour phase is inerted and other temperature ranges where it is not. 42

Halogenated compounds 43

The difference between boiling point and flash point may be lower than with non-halogenated 44

compounds. 45

It is highly recommended to run the tests under careful control with manual observation. 46



Test results may be very difficult to reproduce. In such cases, classification should be based on 1

the lowest value found (flash or burning inside or outside the cup) or on the value obtained 2

during the screening run if in the main trial performed in accordance with the standard, no flash 3

could be found. 4

2.6.4.4.2. Evaluation of hazard information 5

Flash points determined by testing or from the mentioned internationally recognised qualified 6

literature are to be preferred over those derived by calculation because of the error of most of 7

the QSAR methods and their limited application range. 8

If in literature different flash points are found for the same substance the one found as 9

evaluated or recommended has to be preferred. 10

If in literature different flash points are found for the same substance where none is found as 11

evaluated/recommended the lower one has to be preferred because of safety reasons or an 12

experimental determination should be carried out. 13

According to the criteria either Category 1, Category 2 or Category 3, including the relevant 14

hazard statement and signal word, have to be assigned (see Section 2.6.5). In case the criteria 15

for EUH018, EUH209 or EUH209A are met, the liquid has to be labelled with the respective 16

supplemental hazard statement as well. In the majority of cases EUH018 covers EUH209 and 17

EUH209A. 18


Compared to the decision logic 2.6 for flammable liquids contained in the GHS chapter 2.6.4.1, 20

this decision logic below is amended to include derogations for gas oil, diesel, light heating, 21

sustained combustibility and for phrases EUH018, EUH209 and EUH209A. 22

NOTE: The person responsible for the classification of flammable liquids should be

experienced in this field and be familiar with the criteria for classification. 23

76



Figure 2.6.4—a Amended GHS decision logic for flammable liquids to include derogations for 1 gas oil, diesel, light heating, sustained combustibility and for phrases EUH018, EUH209 and 2 EUH209A 3

4

The substance or mixture is a liquid

Flash point ≤ 60 °C

Gas oil, diesel, light heating oil with flash

point up to 75 °C

Halogenated substance, mixture

containing halogenated, volatile

or non volatile flammable

substances

Not subject of hazard class

‘flammable liquid

Category 3

Warning

Flash point < 23 °C Explosive vapour/air

mixture possible (EN 1839, EN 15794)

Sustained combustibility

Flash point > 35 °C

No need to be classified as ‘flammable liquid’

EUH209, EUH209A, EUH018

Category 2

Danger

Boiling point ≤ 35 °C

Category 1

Danger

Yes

Yes Yes

Yes

Yes

Yes

Yes

Yes

No No

No

No

No

No

No

No

No



2.6.5. Hazard communication for flammable liquids 1


statements 3


Label elements for flammable liquids


GHS Pictograms

Signal Word Danger Danger Warning

Hazard

Statement

H224: Extremely

flammable liquid and

vapour

H225: Highly

flammable liquid and

vapour

H226: Flammable liquid

and vapour

Precautionary

Statement

Prevention

P210

P233

P240

P241

P242

P243

P280

P210

P233

P240

P241

P242

P243

P280

P210

P233

P240

P241

P242

P243

P280

Precautionary

Statement

Response

P303 + P361 + P353

P370 + P378

P303 + P361 + P353

P370 + P378

P303 + P361 + P353

P370 + P378

Precautionary

Statement

Storage

P403 + P235 P403 + P235 P403 + P235

Precautionary

Statement

Disposal

P501 P501 P501


2.6.5.2. Additional labelling provisions for flammable liquids 5

Annex II: 1.1.4. EUH018 – 'In use, may form flammable/explosive vapour-air

mixture'

For substances and mixtures not classified as flammable themselves, which may form

flammable/explosive vapour-air mixtures. For substances this might be the case for

halogenated hydrocarbons and for mixtures this might be the case due to a volatile

flammable component or due to the loss of a volatile non-flammable component.

78



Substances or mixtures which do not show a flash point but do have an explosion range or may 1

become flammable in use have to be labelled with EUH018. 2

Annex II: 2.9. Liquid mixtures containing halogenated hydrocarbons

For liquid mixtures which show no flashpoint or a flashpoint higher than 60 ˚C but not more

than 93 ˚C and contain a halogenated hydrocarbon and more than 5 % highly flammable or

flammable substances, the label on the packaging shall bear one of the following statements,

depending on whether the substances referred to above are highly flammable or flammable:

EUH209 — ‘Can become highly flammable in use’ or

EUH209A — ‘Can become flammable in use’

Note: EUH209 and EUH209A are limited to special types of mixtures whereas EUH018

covers a wider range of mixtures. In the majority of cases EUH018 covers EUH209 and

EUH209A. Information about testing can be found in Section 2.6.4.4.1 paragraph 5.

2.6.6. Re-classification of substances and mixtures classified as flammable 3

liquids according to DSD and DPD or already classified for transport 4

2.6.6.1. Relation to transport classification 5

Class 3 of the UN RTDG Model Regulations and the modal transport regulations (ADR, RID, ADN 6

and IMDG Code, ICAO TI) cover flammable liquids based on the same criteria as the CLP hazard 7

class flammable liquid. In general there is a correspondence between transport packing groups 8

and CLP hazard categories. However, in many cases specific exceptions apply. Further, the UN 9

RTDG Model Regulations cover substances and mixtures transported above their flash point and 10

desensitized explosives. In practice the information on flash point and boiling point needed for 11

classification is available and it is recommended to classify based on the data rather than use 12

direct translation. See Annex VII for additional information on transport classification in relation 13

to CLP classification. 14

2.6.7. Examples of classification for flammable liquids 15


criteria 17

2.6.7.1.1. Example 1 18

Mixture of: n-Butylacetate + p-Xylene + 1,3,5-Trimethylbenzene

(7.9 mol % + 60.3 mol % + 31.7 mol %)

Initial boiling point (calculated): 140 °C

Flash point (calculated): 26 °C

calculated flash point is within 5 °C to the limiting value of 23 °C

flash point has to be measured.

Dyn. Viscosity at 20 °C (DIN 53019): 8 mPas

Flash point (EN ISO 3679): 30.0 °C

According to boiling point and measured flash point result: Flam.Liq. Category 3



2.6.7.1.2. Example 2 1

Hydrocarbons and dichloromethane (70 vol % + 30 vol %)

Initial Boiling point (calculated): 52 °C

Flash point: no flash point according to a standard

Because the hydrocarbon part of the mixture has a flash point by itself (- 12 °C) the question ‘Is

an explosive vapour/air mixture possible’ (EN 1839 as amended, EN 15794 as amended) or ‘Can it become highly flammable / flammable during use?’ has to be answered.

Answer: Yes an explosion range exists; yes it can become highly flammable during use.

According to the answer, the mixture has to be labelled with EUH018 or EUH209

Note 1: In that case EUH018 covers EUH209

Note 2: The EUH018 must only be assigned if the substance or mixture is classified as hazardous

(Article 25 (1) of CLP)

Cannot be classified as flammable liquid because the mixture has no flash point.

2.6.7.2. Examples of substances and mixtures not fulfilling the 2


2.6.7.2.1. Example 3 4

Aqueous formulation of aliphatic polyurethane resin

Boiling point (EC 440/2008, EU test method A.2): 92 °C

Dyn. Viscosity at 20 °C (DIN 53019 as amended): 1938 mPas

Sample is highly viscous, use low heating rate for flash point determination (1 °C /min).

Flash point (EN ISO 13736 as amended): 42.5 °C

Sustained combustibility test (UN- MTC L.2) at 60.5 °C: combustion not sustained

Sustained combustibility test (UN-MTC L.2)at 75 °C: combustion not sustained

According to the flash point result: Category 3

However, does not necessarily have to be classified as flammable liquid Category 3 because it did not sustain combustion.

2.6.8. References 5

Brandes, E. and Möller, W.: Safety Characteristic Data, Volume 1, Flammable gases and liquids, 6

nw-Verlag, 2008 7

William M. Haynes et al. (2012) CRC Handbook of Chemistry and Physics 93rd Edition. CRC 8

Press, Taylor and Francis, Boca Raton, FL 9

O'Neil, Maryadele J. et al. © (2016, 2012) The Merck Index - An Encyclopedia of Chemicals, 10

Drugs, and Biologicals (14th Edition – Version 14.9). Merck Sharp & Dohme Corp., a subsidiary 11

of Merck & Co., Inc. 12

13

80



2.7. FLAMMABLE SOLIDS 1


The criteria for ‘Flammable solids’ are found in Annex I, Section 2.7 of CLP and are identical to 3

those in Chapter 2.7 of GHS10. 4


flammable solids 6

Special consideration on particle size 7

The finer the particle size of a solid substance or mixture, the greater the area exposed to air 8

will be, and since flammability is a reaction with the oxygen in air, the particle size will greatly 9

influence the ability to ignite. Hence it is very important that flammable properties for solids are 10

investigated on the substance or mixture as it is actually presented (including how it can 11

reasonably be expected to be used, see Article 8 (6) of CLP). This is indicated by the Note cited 12

in CLP Annex I, 2.7.2.3.For further information please see Section 1.2 within this Guidance. 13


Explosives, organic peroxides, self-reactive substances and mixtures as well as pyrophoric or 15

oxidising solids should not be considered for classification as flammable solids since flammability 16

is an intrinsic hazard in these classes. 17

However, flammable solids can present other physical hazards at the same time, i.e. they might 18

be self-heating or corrosive or emit flammable gases in contact with water. 19

For flammable solids that are packaged in aerosol dispensers, see Section 0, Aerosols. If 20

classified as flammable aerosols, they must not be classified as flammable solids in addition 21

(see Section 0). 22


Annex I: 2.7.1.1.

A flammable solid means a solid which is readily combustible, or may cause or contribute to

fire through friction.

Readily combustible solids are powdered, granular, or pasty substances or mixtures which are

dangerous if they can be easily ignited by brief contact with an ignition source, such as a

burning match, and if the flame spreads rapidly.

Annex I: 2.7.2.3.

[…]

Note 1:

The test shall be performed on the substance or mixture in its physical form as presented. If

for example, for the purposes of supply or transport, the same chemical is to be presented in

a physical form different from that which was tested and which is considered likely to

materially alter its performance in a classification test, the substance shall also be tested in

the new form.

[…]



2.7.4. Classification of substances and mixtures as flammable solids 1


For the classification of a substance or mixture as a flammable solid data on the following 3

properties are needed: 4

melting point; 5

information on water reactivity; 6

information on flash point for solids containing flammable liquids. 7

See also IR & CSA, Chapter R.7a: Endpoint specific guidance, Section R.7.1.2 (Melting/freezing 8

point), R.7.1.9 (Flash point). 9

Many organic solid substances or mixtures fulfil the criteria to be classified as flammable solids. 10

For inorganic solids, the classification as flammable is rather rare. 11


In general, a possible classification as a flammable solid should be considered for any solid 13

organic substance or mixture containing such material. For inorganic material, testing may be 14

waived in cases where the substance is commonly known to be not flammable (i.e. stable salts 15

or metal oxides) or where a flammability hazard can be excluded by any other scientific 16

reasoning. In many cases, a simple screening test (see Section 2.7.4.4) can be used to 17

determine whether a solid should be classified as flammable. Solid substances and mixtures are 18

classified as flammable according to their burning behaviour. 19

The test method as described in Part III, Sub-section 33.2.1.4.3.1 in the UN-MTC should be 20

applied for screening purposes. Alternatively, the burning index (referred to as ‘class number’ in 21

VDI 2263) as obtained from the Burning Behaviour test (VDI 2263, part 1) may be used. If a 22

burning index of 3 or less is found, the substance or mixture should not be classified as a 23

flammable solid and no further testing is required. However, if smouldering or a flame is 24

observed, the full test must be carried out. 25


The classification criteria are fully in accordance with the GHS system. 27

Annex I: 2.7.2.1. Powdered, granular or pasty substances or mixtures (except powders of

metals or metal alloys – see 2.7.2.2) shall be classified as readily combustible solids when

the time of burning of one or more of the test runs, performed in accordance with the test

method described in Part III, sub-section 33.2.1, of the UN RTDG, Manual of Tests and

Criteria, is less than 45 seconds or the rate of burning is more than 2,2 mm/s.

2.7.2.2. Powders of metals or metal alloys shall be classified as flammable solids when they

can be ignited and the reaction spreads over the whole length of the sample in 10 minutes

or less.

2.7.2.3. A flammable solid shall be classified in one of the two categories for this class using

Method N.1 as described in 33.2.1 of the UN RTDG, Manual of Tests and Criteria in

accordance with Table 2.7.1;

28

82



Table 2.7.1

Criteria for flammable solids

Category Criteria

1

Burning rate test

Substances and mixtures other than metal powders:

(a) wetted zone does not stop fire and

(b) burning time < 45 seconds or burning rate > 2,2 mm/s

Metal powders:

burning time 5 minutes

2

Burning rate test

Substances and mixtures other than metal powders:

(a) wetted zone stops the fire for at least 4 minutes and

(b) burning time < 45 seconds or burning rate > 2,2 mm/s

Metal powders:

burning time > 5 minutes and 10 minutes

[…]

Note 2:

Aerosols shall not be classified as flammable solids; see section 2.3.


For safety reasons, it is advisable to test for explosive and self-reactive properties first and to 2

rule out pyrophoric behaviour before performing this test. The classification test is described in 3

Part III, Sub-section 33.2.1.4.3.2 of the UN-MTC. The sample should be tested in its 4

commercially relevant form. Special care has to be taken that the sample forms an unbroken 5

strip or powder train in the test mould. Large pieces that do not fit into the mould should be 6

gently crushed. For pasty or sticking substances it may be helpful to line the mould with a thin 7

plastic foil which is withdrawn after having formed the train. Classification is based upon the 8

fastest burning rate / shortest burning time obtained in six test runs, unless a positive result is 9

observed earlier. For substances and mixtures other than metal powders, the category is 10

assigned depending on whether the wetted zone is able to stop the flame. 11


Classification of flammable solids is done according to decision logic 2.7.4 as included in the 13

GHS. 14

NOTE: The person responsible for the classification of flammable solids should be




Figure 2.7.4—a Decision logic for flammable solids (Decision logic 2.7 of GHS) 1

2

3

Screening test

Burning rate test:

a. For substances or mixtures other than metal powders:

Burning time < 45 s or burning rate > 2.2 mm/s?

b. Metal powders: Burning time 10 min?

Not classified

Category 1

Danger

The substance/mixture is a solid

a. For substances or mixtures other than metal powders:

Does the wetted zone stop propagation of the flame?

b. Metal powders: Burning time > 5 min?

Not classified

Category 2

Warning

Negative

No

No

Positive

Yes

Yes

84



2.7.5. Hazard communication for flammable solids 1


statements 3


Label elements for flammable solids

Classification Category 1 Category 2

GHS Pictograms

Signal Word Danger Warning

Hazard Statement H228: Flammable Solid H228: Flammable Solid

Precautionary Statement Prevention

P210

P240

P241

P280

P210

P240

P241

P280

Precautionary Statement Response P370 + P378 P370 + P378

Precautionary Statement Storage




Division 4.1 within Class 4 of the UN RTDG Model Regulations covers flammable substances, 6

solid desensitized explosives and self-reactive liquids or solids. If a transport classification 7

according to the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) is 8

available it should be kept in mind that transport classification is based on prioritisation of 9

hazards (see UN RTDG Model Regulations, Section 2.0.3) and that flammable solids have a 10

relatively low rank in the precedence of hazards. Therefore, the translation from transport 11

classification to CLP should be only done if a transport classification for a flammable solid is 12

explicitly available. The conclusion that a substance or mixture not classified as a flammable 13

solid for transport should not be classified as a flammable solid according to CLP is, in general, 14

not correct. See Annex VII for additional information on transport classification in relation to 15

CLP classification. 16

2.7.7. Examples of classification for flammable solids 17

2.7.7.1. Example of substances and mixtures fulfilling the classification 18

criteria 19

The following example shows a classification based on test data: 20



Test substance: ‘Flammalene’ (organic material, solid):

Screening test (VDI 2263, part 1): burning index: 5 (burning with an open flame or emission of sparks)

Conclusion: Substance is candidate for classification as a flammable solid, further testing required.

UN Test N.1 (Test method for readily

combustible solids):

Burning times for a distance of 100 mm (6 runs): 44

s; 40 s; 49 s; 45 s; 37 s; 41 s.

Shortest burning time is less than 45 s; substance is a flammable solid.

Wetted zone stops the fire, no reignition.

Conclusion: Classify as flammable solid, Category 2.



Many inorganic salts and oxides are not flammable such as NaCl, NaBr, KI, FeO, MnO etc. 3

Urea or phthalic acid anhydride are examples of organic substances that would not be classified 4

as flammable solids. 5

2.7.8. References 6

VDI guideline 2263, part 1, 1990, Test methods for the Determination of the Safety 7

Characteristics of Dusts 8

9

86



2.8. SELF-REACTIVE SUBSTANCES AND MIXTURES 1


The criteria for ‘Self-reactive substances and mixtures’ are found in Annex I, Section 2.8 of CLP 3

and are identical to those in Chapter 2.8 of GHS11. 4

In general, substances or mixtures classified as self-reactive substances and mixtures can 5

decompose strongly exothermically when 50 kg are exposed to temperatures of 75 °C or lower 6

depending on the Self-Accelerating Decomposition Temperature (SADT) of the substance or 7

mixture. 8

Self-reactive substances and mixtures display a very wide range of properties. The most 9

hazardous type is TYPE A of self-reactive substances and mixtures that are too dangerous to 10

transport commercially though they can be stored safely with appropriate precautions. At the 11

other end of the scale this classification includes substances and mixtures that only decompose 12

slowly at temperatures well above the normal storage and transport temperatures (e.g. 75 °C). 13

The decomposition of self-reactive substances and mixtures can be initiated by heat, contact 14

with catalytic impurities (e.g. acids, heavy-metal compounds, and bases), friction or impact. 15

The rate of decomposition increases with temperature and varies with the substance or mixture. 16

Decomposition, particularly if no ignition occurs, may result in the evolution of toxic gases or 17

vapours. For certain self-reactive substances and mixtures, the temperature must be controlled 18

during storage and handling. Some self-reactive substances and mixtures may decompose 19

explosively, particularly if confined. This characteristic may be modified by the addition of 20

diluents or by the use of appropriate packaging. Some self-reactive substances and mixtures 21

burn vigorously. Self-reactive substances are, for example, some compounds of the types listed 22

below: 23

a. Aliphatic azo compounds (-C-N=N-C-); 24

b. Organic azides (-C-N3); 25

c. Diazonium salts (-CN2+Z-); 26

d. N-nitroso compounds (-N-N=O); and 27

e. Aromatic sulfohydrazides (-SO2-NH-NH2). 28

This list is not exhaustive and substances with other reactive groups, combination of groups and 29

some mixtures of substances may have similar properties. Additional guidance on substances, 30

which may have self-reactive properties, is given in Appendix 6, Section 5.1 of the UN-MTC. 31

Additional hazardous properties, resulting in subsidiary labelling, are indicated in the list of 32

already classified self-reactive substances and mixtures included in the UN RTDG Model 33

Regulations, Section 2.4.2.3.2.3. 34

Commercial self-reactive substances and mixtures are commonly formulated by dilution with 35

solid and liquid substances with which they are compatible. 36

2.8.2. Definitions and general considerations for the classification of self-37

reactives 38

In CLP the following definition is given for self-reactive substances and mixtures: 39




Annex I: 2.8.1.1. Self-reactive substances or mixtures are thermally unstable liquid or solid

substances or mixtures liable to undergo a strongly exothermic decomposition even without

participation of oxygen (air). This definition excludes substances and mixtures classified

according to this Part as explosives, organic peroxides or as oxidising.

2.8.1.2. A self-reactive substance or mixture is regarded as possessing explosive properties

when in laboratory testing the formulation is liable to detonate, to deflagrate rapidly or to

show a violent effect when heated under confinement.

General considerations 1


Type G has no hazard communication elements assigned but shall be considered for

properties belonging to other hazard classes.


Neither the burning properties nor the sensitivity to impact and friction form part of the 3

classification procedure for self-reactive substances and mixtures in CLP. These properties may 4

be of importance in safe handling of self-reactive substances and mixtures (see additional tests 5

in Section 2.8.4.3.2). 6

In addition, the following should be noted: 7

Explosive properties 8

The explosive properties do not have to be determined according to the CLP Annex I, Chapter 9

2.1, because explosive properties are incorporated in the decision logic for self-reactive 10

substances and mixtures. Note that substances and mixtures may have explosive properties 11

when handled under higher confinement. 12

2.8.4. Classification of substances and mixtures as self-reactive 13


The classification of a self-reactive substance or mixture in one of the seven categories ‘types A 15

to G’ is dependent on its detonation, deflagration and thermal explosion properties, its response 16

to heating under confinement, its explosive power and the concentration and the type of diluent 17

added to desensitize the substance or mixture. Specifications of acceptable diluents that can be 18

used safely are given in the UN RTDG Model Regulations, Section 2.4.2.3.5. 19

The classification of a self-reactive substance or mixture as type A, B or C is also dependent on 20

the type of packaging in which the substance or mixture is tested as it affects the degree of 21

confinement to which the substance or mixture is subjected. This has to be considered when 22

handling the substance or mixture; stronger packaging may result in more violent reactions 23

when the substance or mixture decomposes. This is why it is important that storage and 24

transport is done in packaging, allowed for the type of self-reactive substance and mixture, that 25

conforms the requirements of the UN-packaging or IBC instruction (P520/IBC520) or tank 26

instruction (T23). 27

The traditional aspects of explosive properties, such as detonation, deflagration and thermal 28

explosion, are incorporated in the decision logic Figure 2.8.1 of CLP (see Section 2.8.4.4). 29

Consequently, the determination of explosive properties as prescribed in the hazard class 30

explosives needs not to be conducted for self-reactive substances and mixtures. 31

88




According to CLP, substances and mixtures must be considered for classification in this hazard 2

class as a self-reactive substance or mixture unless: 3

Annex I: 2.8.2.1. […]

(a) they are explosives, according to the criteria given in 2.1;

(b) they are oxidising liquids or solids, according to the criteria given in 2.13 or 2.14, except

that mixtures of oxidising substances, which contain 5 % or more of combustible organic

substances shall be classified as self-reactive substances according to the procedure defined

in 2.8.2.2;

(c) they are organic peroxides, according to the criteria given in 2.15;

(d) their heat of decomposition is less than 300 J/g; or

(e) their self-accelerating decomposition temperature (SADT) is greater than 75 °C for a 50

kg package (See UN RTDG, Manual of Test and Criteria, sub-sections 28.1, 28.2, 28.3 and

Table 28.3.)

2.8.2.2. Mixtures of oxidising substances, meeting the criteria for classification as oxidising

substances, which contain 5 % or more of combustible organic substances and which do not

meet the criteria mentioned in (a), (c), (d) or (e) in 2.8.2.1, shall be subjected to the self-

reactive substances classification procedure;

Such a mixture showing the properties of a self-reactive substance type B to F (see 2.8.2.3)

shall be classified as a self-reactive substance.

[…]

In addition to the above, substances and mixtures must be considered for classification in this 4

hazard class unless: 5

Annex I: 2.8.4.2.

[…]

(a) There are no chemical groups present in the molecule associated with explosive or self-

reactive properties; examples of such groups are given in Tables A6.1 and A6.2 in

Appendix 6 of the UN RTDG, Manual of Tests and Criteria.

[…]

In the CLP decision logic (see Section 2.8.4.4), classification of self-reactive substances or 6

mixtures is based on performance based testing in both small scale tests and, where necessary, 7

some larger scale tests with the substance or mixture in its packaging. The concept of ‘intrinsic 8

properties’ is, therefore, not necessarily, applicable to this hazard class. 9

Self-reactive substances or mixtures are classified in one of the seven categories of ‘types A to 10

G’ according to the classification criteria given in Section 2.8.2.3 of Annex I, CLP. The 11

classification principles are given in the decision logic in Figure 2.8.1 of CLP (see Section 12

2.8.4.4) and the Test Series A to H, as described in the Part II of the UN-MTC, should be 13

performed. 14



Annex I: 2.8.2.3. Self-reactive substances and mixtures shall be classified in one of the

seven categories of ‘types A to G’ for this class, according to the following principles:

(a) any self-reactive substance or mixture which can detonate or deflagrate rapidly, as

packaged, shall be defined as self-reactive substance TYPE A;

(b) any self-reactive substance or mixture possessing explosive properties and which, as

packaged, neither detonates nor deflagrates rapidly, but is liable to undergo a thermal

explosion in that package shall be defined as self-reactive substance TYPE B;

(c) any self-reactive substance or mixture possessing explosive properties when the substance

or mixture as packaged cannot detonate or deflagrate rapidly or undergo a thermal

explosion shall be defined as self-reactive substance TYPE C;

(d) any self-reactive substance or mixture which in laboratory testing:

(i) detonates partially, does not deflagrate rapidly and shows no violent effect when

heated under confinement; or

(ii) does not detonate at all, deflagrates slowly and shows no violent effect when


(iii) does not detonate or deflagrate at all and shows a medium effect when heated

under confinement;

shall be defined as self-reactive substance TYPE D;

(e) any self-reactive substance or mixture which, in laboratory testing, neither detonates nor

deflagrates at all and shows low or no effect when heated under confinement shall be

defined as self-reactive substance TYPE E;

(f) any self-reactive substance or mixture which, in laboratory testing, neither detonates in

the cavitated state nor deflagrates at all and shows only a low or no effect when heated

under confinement as well as low or no explosive power shall be defined as self-reactive

substance TYPE F;

(g) any self-reactive substance or mixture which, in laboratory testing, neither detonates in

the cavitated state nor deflagrates at all and shows no effect when heated under

confinement nor any explosive power, provided that it is thermally stable (SADT is 60 oC

to 75 oC for a 50 kg package), and, for liquid mixtures, a diluent having a boiling point not

less than 150 oC is used for desensitisation shall be defined as self-reactive substance

TYPE G. If the mixture is not thermally stable or a diluent having a boiling point less than

150 oC is used for desensitisation, the mixture shall be defined as self-reactive substance

TYPE F.

Where the test is conducted in the package form and the packaging is changed, a further test

shall be conducted where it is considered that the change in packaging will affect the outcome

of the test.

A list of currently classified self-reactive substances and mixtures is included in the UN RTDG 1

Model Regulations, Section 2.4.2.3.2.3. 2


2.8.4.3.1. Thermal stability tests and temperature control 4

In addition to the classification tests given in decision logic Figure 2.8.1 of CLP, the thermal 5

stability of the self-reactive substances and mixtures has to be assessed in order to determine 6

the SADT. 7

90



The SADT is defined as the lowest temperature at which self-accelerating decomposition of a 1

substance or mixture may occur in the packaging as used in transport, handling and storage. 2

The SADT is a measure of the combined effect of the ambient temperature, decomposition 3

kinetics, package size and the heat transfer properties of the substance or mixture and its 4

packaging. 5

There is no relation between the SADT of a self-reactive substance and mixture and its 6

classification in one of the seven categories ‘types A to G’. The SADT is used to derive safe 7

handling, storage and transport temperatures (control temperature) and alarm temperature 8

(emergency temperature). 9

Depending on its SADT a self-reactive substance and mixture needs temperature control and 10

the rules as given in CLP Annex I, 2.8.2.4, consist of the following two elements: 11

1. Criteria for temperature control: 12

2. Self-reactive substances and mixtures need to be subjected to temperature control when 13

the SADT is ≤ 55 ° C. 14

3. Derivation of control and emergency temperatures: 15

Type of receptacle SADT* Control temperature Emergency temperature

Single packagings and IBC’s

20 °C or less

over 20 °C to 35 °C

over 35 °C

20 °C below SADT

15 °C below SADT

10 °C below SADT

10 °C below SADT

10 °C below SADT

5 °C below SADT

Tanks < 50 °C 10 °C below SADT 5 °C below SADT

*i.e. the SADT of the substance/mixture as packaged for transport, handling and storage. 16

It should be emphasized that the SADT is dependent on the nature of the self-reactive 17

substance or mixture itself, together with the volume and heat-loss characteristics of the 18

packaging or vessel in which the substance or mixture is handled. The temperature at which 19

self-accelerating decomposition occurs falls: 20

as the size of the packaging or vessel increases; and 21

with increasing efficiency of the insulation on the package or vessel. 22

The SADT is only valid for the substance or mixture as tested and when handled properly. 23

Mixing the self-reactive substances and mixtures with other chemicals, or contact with 24

incompatible materials (including incompatible packaging or vessel material) may reduce the 25

thermal stability due to catalytic decomposition, and lower the SADT. This may increase the risk 26

of decomposition and has to be avoided. 27

2.8.4.3.2. Additional considerations and testing 28


The sensitivity of self-reactive substances and mixtures to impact (solids and liquids) and 30

friction (solids only) may be of importance for the safe handling of the substances and mixtures, 31

in the event that these substances and mixtures have pronounced explosive properties (e.g. 32

rapid deflagration and/or violent heating under confinement). Test methods to determine these 33

properties are described in Test Series 3 (a) (ii) and 3 (b) (i) of the UN-MTC. This information 34

should be documented in the SDS. 35

Burning properties 36

Although there are currently no dedicated storage guidelines for self-reactive substances and 37

mixtures (although in some countries under development), often the regulations for organic 38



peroxides are referred to. For storage classification the burning rate is commonly used, see 1

Section 2.15 on organic peroxides. 2

Flash point 3

The flash point for liquid self-reactive substances or mixtures is only relevant in the 4

temperature range where the product is thermally stable. Above the SADT of the self-reactive 5

substance or mixture, flash point determination is not relevant because decomposition products 6

are evolved. 7

NOTE: In case a flash point determination seems reasonable (expected flash point below

the SADT) a test method using small amount of sample is recommended. In case the self-

reactive substance or mixture is diluted or dissolved, the diluent may determine the flash

point.

Auto-ignition temperature 8

The determination of the auto ignition temperature is not relevant for self-reactive substances 9

and mixtures, because the vapours decompose during the execution of the test. Available test 10

methods are for non-decomposing vapour phases. Auto ignition of self-reactive substance and 11

mixtures vapours when they decompose, can never be excluded. This information should be 12

documented in the SDS. 13

Self-ignition temperature 14

Also self-ignition temperature determination (test applicable for solids) is not relevant. The 15

thermal stability of self-reactive substances and mixtures is quantitatively given by the SADT 16

test. 17

Control and Emergency temperatures 18

The Control and Emergency temperatures are based on the SADT as determined by UN Test 19

H.4. The Dewar vessel used in the UN Test H.4 is supposed to be representative for the 20

substance or mixture handled in packages. For handling of the substance or mixture in larger 21

quantities (IBCs/tanks/vessels etc.) and/or in better (thermally) insulated containers under 22

more thermal insulated conditions, the SADT has to be determined for that quantity with the 23

given degree of insulation. From that SADT the Control and Emergency temperatures can be 24

derived (see also Section 0) 25

2.8.4.3.3. Additional classification considerations 26

Currently, the following properties are not incorporated in the classification of self-reactives 27

under the CLP: 28

mechanical sensitivity i.e. impact and friction sensitivity (for handling purposes); 29

burning properties (for storage purposes); 30

flash point for liquids; and 31

burning rate for solids. 32

In addition to the GHS criteria CLP mentions that: 33

Annex I: 2.8.2.2

[…]

Where the test is conducted in the package form and the packaging is changed, a further

test shall be conducted where it is considered that the change in packaging will affect the

outcome of the test.

92



Please note that polymerising substances do not fulfil the criteria for classification as self-1

reactives. However, there are on-going discussions at the UNSCEGHS on this subject. 2


Classification of self-reactive substances and mixtures is done according to decision logic 2.8 as 4

included in the GHS. 5

NOTE: The person responsible for the classification of self-reactive substances and mixtures

should be experienced in this field and be familiar with the criteria for classification.

6



Figure 2.8.4—a Decision logic 2.8 for self-reactive substances and mixtures 1

2

3

94



2.8.5. Hazard communication for self-reactives 1


statements 3

According to CLP the following label elements must be used for substances and mixtures 4

meeting the criteria for this hazard class: 5


Label elements for self-reactive substances and mixtures

Classification Type A Type B Type C & D Type E & F Type G2

GHS pictograms

There are

no label

elements

allocated

to this

hazard

category

Signal Words Danger Danger Danger Warning

Hazard Statement H240:

Heating may

cause an

explosion

H241:

Heating may

cause a fire or

explosion

H242:

Heating may

cause a fire

H242:

Heating

may cause a

fire

Precautionary

statement

Prevention

P210

P234

P235

P240

P280

P210

P234

P235

P240

P280

P210

P234

P235

P240

P280

P210

P234

P235

P240

P280

Precautionary

statement

Response

P370 + P372

+ P380 +

P373

P370 + P380

+ P375

[+P378]1

P370 + P378 P370 + P378

Precautionary

statement

Storage

P403

P411

P420

P403

P411

P420

P403

P411

P420

P403

P411

P420

Precautionary

statement

Disposal

P501 P501 P501 P501



1 See the introduction to Annex IV for details on the use of square brackets.

2 Type G has no hazard communication elements assigned but should be considered for properties belonging to other hazard classes.


2.8.6. Relation to transport classificationaccording to DSD and DPD or 2

already classified for transport 3

Division 4.1 within Class 4 of the UN RTDG Model Regulations covers flammable substances, 4

solid desensitized explosives and self-reactive liquids or solids. A list of already classified self-5

reactive substances is included in UN RTDG Model Regulations, Section 2.4.2.3.2.3. This table 6

includes self-reactive substances of various types from type B to type F. See Annex VII for 7


2.8.7. Examples of classification for self-reactives 9


criteria 11

Substance to be classified: NP 12

Molecular formula: n.a. 13

According to CLP Annex I, Section 2.8.2.1, the substance has: 14

an energy content of 1452 kJ/kg; and 15

a SADT of 45 °C (in 50 kg package); 16

and consequently it has to be considered for classification in the hazard class self-reactive 17

substances and mixtures. 18

Test results and classification according to CLP decision logic 2.8.1 for self-reactive substances 19

and mixtures and the UN - MTC, Part II, is as follows: 20

21

CLASSIFICATION TEST RESULTS

1. Name of the self-reactive substance or mixture: NP

2. General data

2.1. Composition NP, technically pure

2.2. Molecular formula n.a.

2.3. Physical form solid, fine powder

2.4. Colour brown

2.5. Density (apparent) 460 kg/m3

3. Detonation (test series A)

Box 1 of the decision logic Does the substance propagate a detonation?

3.1. Method UN Test A.1: BAM 50/60 steel tube test

3.2. Sample conditions technically pure substance

3.3. Observations fragmented part of the tube: 12, 18cm

96




3.4. Result No

3.5. Exit 1.3

4. Deflagration (test series C)

Box 5 of the decision logic Does the substance propagate a deflagration?

4.1. Method 1 Time/pressure test (test C.1)

4.1.1. Sample conditions ambient temperature

4.1.2. Observations 498, 966, 3395 ms

4.1.3. Result Yes, slowly

4.2. Method 2 Deflagration test (test C.2)

4.2.1. Sample conditions temperature: 20 °C

4.2.2. Observations deflagration rate: 0.90, 0.87 mm/s

4.2.3. Result Yes, slowly

4.3. Final result Yes, slowly

4.4. Exit 5.2

5. Heating under confinement (test series E)

Box 8 of the decision logic: What is the effect of heating it under defined confinement?

5.1. Method 1 Koenen test (test E.1)

5.1.1. Sample conditions

5.1.2. Observations Limiting diameter: < 1.0 mm

fragmentation type ‘A’

5.1.3. Result Low

5.2. Method 2 Dutch pressure vessel test

(test E.2)

5.2.1. Sample conditions

5.2.2. Observations Limiting diameter: <1.0 mm (with 10 g), 1.0 mm

(50 g)

5.2.3. Result low

5.3. Final result low

5.4. Exit 8.3

6. Thermal stability (outside of the decision logic)

6.1. Method Heat accumulation storage test (test H.4)

6.2. Sample conditions : mass 232.5 g. Half life time of cooling of Dewar

vessel with

400 ml water: 10.0 hrs.(representing substance in package)

6.3. Observations self-accelerating decomposition at 45 °C

no self-accelerating decomposition at 40 °C




6.4. Result SADT 45 °C (in 50 kg package)

7. General remarks The decision logic is given in Figure 2.8.7—a

8. Final classification

Hazard / hazard class: Self-reactive substance, Type D, solid, temperature controlled

Label Flame (GHS02)

Signal word Danger

Hazard statement H242: Heating may cause a fire

Temperature control Needed based on SADT (45 °C, in package)

Control temperature* 35 °C (in package)

Emergency temperature* 40 °C (in package)

*See UN-MTC, table 28.2. 1

2

98



Figure 2.8.7—a Decision logic for self-reactive substance example: NP, technically pure 1

2

3



2.9. PYROPHORIC LIQUIDS 1


The criteria for ‘Pyrophoric liquids’ are found in Annex I, Section 2.9 of CLP and are identical to 3


Pyrophoricity, i.e. the ability to spontaneously ignite in air, is the result of a reaction of a 5

substance or mixture with the oxygen in the air. The reaction is exothermic and has the 6

particularity that it starts spontaneously, i.e. without the aid of a supplied spark, flame, heat or 7

other energy source. Another way of saying this is that the auto-ignition temperature for a 8

pyrophoric substance or mixture is lower than room (ambient) temperature. 9

Organo-metals and organo-metalloids may be suspected of being pyrophores, as well as their 10

derivatives. Also organo-phosphines and their derivatives, hydrides and their derivatives and 11

haloacetylene derivatives may show pyrophoricity (Urben, 2007). 12

There are also pyrophoric substances or mixtures that do not belong to the above mentioned 13

groups of chemicals, i.e. the list above is not exhaustive. Since pyrophoric substances or 14

mixtures ignite spontaneously in air, pyrophoricity is a very dangerous property. In case of 15

doubt it should therefore be thoroughly investigated whether a given substance or mixture is 16

pyrophoric. More information on pyrophoric substances can e.g. be found in Bretherick’s 17

Handbook of Reactive Chemical Hazards (Urben, 2007). 18

2.9.2. Definitions and general considerations for the classification pyrophoric 19

liquids 20

The definition in CLP for pyrophoric liquids is as follows: 21

Annex I: 2.9.1. Definition

Pyrophoric liquid means a liquid substance or mixture which, even in small quantities, is

liable to ignite within five minutes after coming into contact with air.


Pyrophoric substances and mixtures will react spontaneously with air already in small amounts 23

and more or less instantaneously (within minutes). This differentiates them from self-heating 24

substances and mixtures, which also react spontaneously with air but only when in larger 25

amounts and after an extended period of time (hours or days). While liquids in themselves 26

generally do not exhibit self-heating properties due to the limited contact with air (which can 27

occur only at the surface), liquids that are adsorbed onto solid particles should, in general, be 28

considered for classification in the hazard class self-heating substances and mixtures, see 29

Chapter 2.11 of this guidance. 30

Pyrophoricity may be expected for certain reactive metals and some of their compounds (e.g. 31

hydrides and other organo-metal compounds). Many of these substances and mixtures will also 32

react vigorously with water under the production of flammable gases. Such substances and 33

mixtures may thus be classified in the hazard class substances and mixtures which in contact 34

with water emit flammable gases in addition, see Chapter 2.12 of this guidance. It should be 35

noted in this context that water-reactive substances and mixtures may also to some extent 36

react with the humidity in air, although such a reaction is seldom vigorous. A substance or 37


100



mixture that spontaneously ignites in air in accordance with the test procedures is to be 1

considered pyrophoric, regardless of the reaction mechanism. 2

Liquids not classified as pyrophoric but that can burn may belong to the hazard class flammable 3

liquids depending on their flash point and ability to sustain combustion, see Chapter 0 of this 4

guidance. 5

2.9.4. Classification of substances and mixtures as pyrophoric liquids 6


Since the tests to determine pyrophoricity are simple and require no special equipment, see 8

Section 2.9.4.4 below, there is in general no reason to go to data sources instead of performing 9

tests. Furthermore, the possibilities of waiving tests are ample both for known pyrophores and 10

for substances and mixtures known not to be pyrophoric, see Section 2.9.4.2 below. If 11

information anyway is taken from literature or other data sources, it is of utmost importance 12

that the correct physical form is considered, see Section 2.0.4. Naturally, all data sources 13

should be carefully evaluated with regard to reliability and scientific validity. 14


In case a liquid is known from practical handling to be pyrophoric no testing is necessary. Such 16

liquids are classified as pyrophoric liquids without testing. This would also be the case if the 17

liquid spontaneously ignites upon opening of the receptacle when trying to perform the tests for 18

classification. 19

According to the additional classification considerations in CLP Annex I, 2.9.4, the classification 20

procedure for pyrophoric liquids need not be applied when experience in manufacture or 21

handling shows that the liquid does not ignite spontaneously on coming into contact with air at 22

normal temperatures (i.e. the liquid is known to be stable at room temperature for prolonged 23

periods of time (days)). 24


Section 2.9.2.1 of Annex I of CLP specifies the classification criteria: 26


Criteria for pyrophoric liquids

Category Criteria

1 The liquid ignites within 5 min when added to an inert carrier and exposed to

air, or it ignites or chars a filter paper on contact with air within 5 min.


In Section 2.9.2.1 of Annex I of CLP reference to the test-methods are made: 28

Annex I: 2.9.2.1. A pyrophoric liquid shall be classified in a single category for this class

using test N.3 in part III, sub-section 33.3.1.5 of the UN RTDG, Manual of Tests and Criteria

according to Table 2.9.1:

The UN Test N.3 for pyrophoricity is quite simple and sufficiently described in Part III, Section 29

33 of the UN-MTC. No special equipment is needed. Essentially the substance or mixture is 30

exposed to air to see if it ignites. For liquids which do not spontaneously ignite when poured, 31



the surface in contact with air is increased using a filter paper. Ignition or charring of the filter 1

paper is regarded as a positive response in the test, i.e. such a liquid is considered to be 2

pyrophoric. 3

It is important that samples for testing of pyrophoric properties are carefully packed and sealed. 4

Furthermore, the material offered for testing should be freshly prepared, since the reactive 5

properties may diminish due to aging or agglomeration. Whenever experiments are to be done 6

one should be careful – a pyrophoric substance or mixture may well ignite already upon opening 7

the receptacle! 8

It should be noted that the mechanism of oxidation is, in general, very complex, and that the 9

humidity of air might influence the rate of reaction. Therefore a false negative may result when 10

performing the tests in an extremely dry environment, and this condition must be avoided when 11

performing the tests for classification for pyrophoricity. The filter paper test of UN Test N.3 for 12

pyrophoric liquids should be carried out at 25 ± 2 °C and a relative humidity of 50 ± 5 % (see 13

UN-MTC, Section 33.3.1.5). 14


Classification of pyrophoric liquids is done according to decision logic 2.9.4.1 as included in the 16

GHS. 17

NOTE: The person responsible for the classification of pyrophoric liquids should be


102



2.9.4.5.1. Decision logic for pyrophoric liquids 1

Figure 2.9.4—a Decision logic for pyrophoric liquids (Decision logic 2.9 of GHS) 2

3

4

5

Does it ignite within 5 min when poured into a porcelain cup filled with diatomaceous earth or silica gel?

The substance/mixture is a liquid

Category 1

Danger

Does it ignite or char a filter paper within 5 min?

Not classified

Category 1

Danger

Yes

Yes

No

No



2.9.5. Hazard communication for pyrophoric liquids 1


statements 3

Annex I: 2.9.3 Table 2.9.2

Label elements for pyrophoric liquids


GHS Pictogram

Signal Word Danger

Hazard Statement H250: Catches fire spontaneously if

exposed to air


P222

P231+P232

P233

P280

Precautionary Statement Response P302 + P334

P370 + P378





Division 4.2 within Class 4 of the UN RTDG Model Regulations covers pyrophoric solids, liquids 6

and self-heating substances and mixtures. UN Test N.3 that is used for classification for 7

pyrophoricity for liquids according to CLP is also used for classification in the subdivision 8

pyrophoric substances and mixtures in Division 4.2: Substances liable to spontaneous 9

combustion according to the UN RTDG Model Regulations. The criteria for Category 1 according 10

to CLP (which is the only category for pyrophoric liquids) and for packing group I in Division 4.2 11

according to the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) are also 12

exactly the same. Furthermore, all pyrophoric substances and mixtures are assigned to packing 13

group I within Division 4.2, which is used exclusively for pyrophoric substances and mixtures. 14

Therefore, any liquid assigned to Division 4.2, packing group I according to the modal transport 15

regulations (ADR, RID, ADN and IMDG Code, ICAO TI) will be classified in Category 1 of the 16

hazard class pyrophoric liquids according to CLP. See Annex VII for additional information on 17

transport classification in relation to CLP classification. 18

104



2.9.7. Examples of classification for pyrophoric liquids 1

Please note that the substance and mixture names in this chapter are fictitious. 2


criteria 4

2.9.7.1.1. Example 1 5

Name: Pyrpherdine

Physical state: Liquid

Pyrophoric properties: Unknown, therefore the UN Test N.3 of the UN-MTC was applied. However, when opening the receptacle in order to perform the test,

Pyrpherdine self-ignited.

Classification: Pyrophoric liquid, Category 1

6

7



2.9.7.1.2. Example 2 1

Name: Qulipyr


Pyrophoric properties: Unknown, therefore the UN Test N.3 of the UN-MTC was applied.

Test result: When poured according to the test procedure, nothing happened. The

procedure was repeated six times, each time giving a negative result (i.e. no ignition). Therefore Qulipyr was supplied to a filter paper in accordance with the test method. In the second trial the filter paper was charred within five minutes.

Classification: Pyrophoric liquid, Category 1



2.9.7.2.1. Example 3 4

Name: Notpyratal


Pyrophoric properties: Unknown, therefore UN Test N.3 of the UN-MTC was applied.

Test result: When poured according to the test procedure nothing happened in either of six trials. Therefore Notpyratal was supplied to a filter paper in accordance with the test method, whereupon no ignition or charring

occurred in either of three trials.

Classification: Not a pyrophoric liquid

2.9.8. References 5

Urben, Peter G. (2007). Bretherick's Handbook of Reactive Chemical Hazards, Volumes 1-2 (7th 6

Edition). Elsevier. 7

8

106



2.10. PYROPHORIC SOLIDS 1


The criteria for ‘Pyrophoric solids’ are found in Annex I, Section 2.10 of CLP and are identical to 3


Pyrophoricity, i.e. the ability to spontaneously ignite in air, is the result of a reaction of a 5

substance or mixture with the oxygen in the air. The reaction is exothermic and has the 6

particularity that it starts spontaneously, i.e. without the aid of a supplied spark, flame, heat or 7

other energy source. Another way of saying this is that the self-ignition temperature for a 8

pyrophoric substance or mixture is lower than room (ambient) temperature. 9

Organo-metals and organo-metalloids may be suspected of being pyrophores, as well as their 10

derivatives. Also organo-phosphines and their derivatives, hydrides and their derivatives, 11

haloacetylene derivatives, and complex acetylides may show pyrophoricity (Urben, 2007). 12

Furthermore, powders or fine particles of metals could be pyrophoric. However, although many 13

solid metallic substances, like e.g. aluminium, would be suspected of being pyrophoric when 14

considering their general reactivity, they form a protective oxide-coat upon reaction with air. 15

This thin coat of metal oxide prevents the metal from reacting further, and hence such 16

substances may not show pyrophoric behaviour in reality. 17

There are also pyrophoric solids that do not belong to the above mentioned groups of 18

chemicals, i.e. the list above is not exhaustive. Since pyrophoric solids ignite spontaneously in 19

air, pyrophoricity is a very dangerous property. In case of doubt it should therefore be 20

thoroughly investigated whether a given solid is pyrophoric. More information on pyrophoric 21

solids can e.g. be found in Bretherick’s Handbook of Reactive Chemical Hazards (Urben, 2007). 22

2.10.2. Definitions and general considerations for the classification pyrophoric 23

solids 24

The definition in CLP for pyrophoric solids is as follows: 25


Pyrophoric solid means a solid substance or mixture which, even in small quantities, is liable

to ignite within five minutes after coming into contact with air.


The finer the particle size of a solid, the greater the area exposed to air will be, and since 27

pyrophoricity is a reaction with the oxygen in air, the particle size will greatly influence the 28

ability to spontaneously ignite. Hence it is very important that pyrophoric properties for solids 29

are investigated on the substance or mixture as it is actually presented (including how it can 30


Annex I: 2.10.2.1.

[…]

Note: The test shall be performed on the substance or mixture in its physical form as

presented. If for example, for the purposes of supply or transport, the same chemical is to

be presented in a physical form different from that which was tested and which is considered

likely to materially alter its performance in a classification test, the substance shall also be

tested in the new form.



reasonably be expected to be used, see Article 8 (6) of CLP). This is indicated by the Note cited 1

in CLP Annex I, 2.10.2.1. 2


Pyrophoric solids will react spontaneously with air already in small amounts and more or less 4

instantaneously (within minutes). This differentiates them from self-heating substances and 5

mixtures, which also react spontaneously with air but only when in larger amounts and after an 6

extended period of time (hours or days). A solid which is not classified as a pyrophoric solid 7

may thus belong to the hazard class self-heating substances and mixtures, and should be 8

considered for classification in that hazard class, see Chapter 2.11 of this guidance. 9

Pyrophoricity may be expected for certain reactive metals and some of their compounds (e.g. 10

hydrides and other organo-metal compounds). Many of these substances will also react 11

vigorously with water under the production of flammable gases. Such substances may thus be 12

classified in the hazard class substances and mixtures which in contact with water emit 13

flammable gases in addition see Chapter 2.12 of this guidance. It should be noted in this 14

context that water-reactive substances or mixtures may also to some extent react with the 15

humidity in air, although such a reaction is seldom vigorous. A substance that spontaneously 16

ignites in air in accordance with the test procedures is to be considered pyrophoric, regardless 17

of the reaction mechanism. 18

Solids not classified as pyrophoric may still be able to burn rapidly if subjected to enough 19

initiating energy, such as the flame from a gas burner, to start the reaction. Therefore they may 20

be subject to classification in the hazard class flammable solids, see Chapter 2.7 of this 21

guidance, i.e. they may be 'readily combustible solids'. 22

2.10.4. Classification of substances and mixtures as pyrophoric solids 23


Since the tests to determine pyrophoricity are simple and require no special equipment, see 25

Section 2.10.4.4 below, there is in general no reason to go to data sources instead of 26

performing tests. Furthermore, the possibilities of waiving tests are ample both for known 27

pyrophores and for substances and mixtures known not to be pyrophoric, see Section 2.10.4.2 28

below. If information is taken from literature or other data sources anyway, it is of utmost 29

importance that the correct physical form is considered, see Section 2.0.4. Naturally, all data 30

sources should be carefully evaluated with regard to reliability and scientific validity. 31


In case a solid is known from practical handling to be pyrophoric no testing is necessary. Such 33

solids are classified as pyrophoric solids without testing. This would also be the case if the solid 34

spontaneously ignites upon opening of the receptacle when trying to perform the tests for 35

classification. 36

According to the additional classification considerations in CLP Annex I, 2.10.4, the classification 37

procedure for pyrophoric solids need not be applied when experience in manufacture or 38

handling shows that the substance or mixture does not ignite spontaneously on coming into 39

contact with air at normal temperatures (i.e. the substance or mixture is known to be stable at 40

room temperature for prolonged periods of time (days)). 41


Section 2.10.2.1 of Annex I of CLP specifies the classification criteria: 43

108




Criteria for pyrophoric solids

Category Criteria

1 The solid ignites within 5 minutes of coming into contact with air.


In Section 2.10.2.1 of Annex I of CLP reference to the test-methods are made: 2

Annex I: 2.10.2.1. A pyrophoric solid shall be classified in a single category for this class

using test N.2 in part III, sub-section 33.3.1.4 of the UN RTDG, Manual of Tests and Criteria

in accordance with Table 2.10.1:

UN Test N.2 for pyrophoricity is quite simple and sufficiently described in Part III, Section 33 of 3

the UN-MTC. No special equipment is needed. Essentially the solid is exposed to air to see if it 4

ignites. 5

It is important that samples for testing of pyrophoric properties are carefully packed and sealed. 6

Furthermore, the material offered for testing should be freshly prepared, since the reactive 7

properties may diminish due to aging or agglomeration. Whenever experiments are to be done 8

one should be careful – a pyrophoric solid may well ignite already upon opening the receptacle! 9

It should be noted that the mechanism of oxidation is, in general, very complex, and that the 10

humidity of air might influence the rate of reaction. It is known that certain metals will not react 11

in dry air, whereas in the presence of moisture the reaction is almost instantaneous (often even 12

trace amounts of moisture are sufficient). Therefore a false negative may result when 13

performing the tests in an extremely dry environment, and this condition must be avoided when 14

performing the tests for classification for pyrophoricity. 15


Classification of pyrophoric solids is done according to decision logic 2.10.4.1 as included in the 17

GHS. 18

NOTE: The person responsible for the classification of pyrophoric solids should be




2.10.4.5.1. Decision logic for pyrophoric solids 1

Figure 2.10.4—a Decision logic for pyrophoric solids (Decision logic 2.10 of GHS) 2

3

4

2.10.5. Hazard communication for pyrophoric solids 5


statements 7

Annex I: 2.10.3 Table 2.10.2

Label elements for pyrophoric solids


GHS Pictogram

Signal Word Danger

Hazard Statement H250: Catches fire spontaneously if

exposed to air


P222

P231+P232

P233

P280

Precautionary Statement Response P302 + P335 + P334

P370 + P378




Does it ignite within 5 min after exposure to air?

The substance/mixture is a solid Category 1

Danger

Not classified

Yes

No

110




Division 4.2 within Class 4 of the UN RTDG Model Regulations covers pyrophoric solids, liquids 2

and self-heating substances and mixtures. The UN Tests N.2 that is used for classification for 3

pyrophoricity for solids according to CLP is also used for classification in the subdivision 4

pyrophoric substances and mixtures in Division 4.2: Substances liable to spontaneous 5

combustion according to the UN RTDG Model Regulations. The criteria for Category 1 according 6

to CLP (which is the only category for pyrophoric solids) and for packing group I in Division 4.2 7

according to the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) are also 8

exactly the same. Furthermore, all pyrophoric substances and mixtures are assigned to packing 9

group I within Division 4.2, which is used exclusively for pyrophoric substances and mixtures. 10

Therefore, any solid substance or mixture assigned to Division 4.2, packing group I according to 11

the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) will be classified in 12

Category 1 of the hazard class pyrophoric solids according to CLP. See Annex VII for additional 13

information on transport classification in relation to CLP classification. 14

2.10.7. Examples of classification for pyrophoric solids 15

Please note that the substance and mixture names in this chapter are fictitious. 16


criteria 18

2.10.7.1.1. Example 1 19

Name: Pyroferil

Physical state: Solid

Pyrophoric properties: Pyroferil is known to self-ignite upon contact with air at ambient conditions.

Classification: Pyrophoric solid, Category 1

2.10.7.1.2. Example 2 20

Name: Zorapyrole


Pyrophoric properties: Unknown, therefore the UN Test N.2 of the UN-MTC was applied.

Test result: When poured from one meter height according to the test procedure, Zorapyrole self-ignited after two minutes already in the first trial.

Classification: Pyrophoric solid, Category 1

21



2.10.7.2.1. Example 3 24

Name: Nonopyr




Pyrophoric properties: Nonopyr has been handled extensively in air and has never self-ignited. From the chemical structure no pyrophoricity is expected.

Classification: Not a pyrophoric solid

2.10.7.2.2. Example 4 1

Name: Pyronot


Pyrophoric properties: Unknown, therefore UN Test N.2 of the UN-MTC was applied.

Test result: When poured from one meter height according to the test procedure no

ignition occurred within five minutes. The procedure was repeated six times

and each time the result was negative.

Classification: Not a pyrophoric solid

2.10.8. References 2



112



2.11. SELF-HEATING SUBSTANCES AND MIXTURES 1


The criteria for ‘Self-heating substances and mixtures’ are found in Annex I, Section 2.11 of CLP 3

and are identical to those in Chapter 2.11 of GHS14. 4

Self-heating is the result of an exothermic reaction of a substance or mixture with the oxygen in 5

the air. Initially, the reaction rate may be very low. However, when the heat produced cannot 6

be removed rapidly enough (i.e. heat accumulation), the substance or mixture will self-heat, 7

with the possible consequence of self-ignition. The phenomenon can occur only where a large 8

surface of substance or mixture is in contact with air or oxygen (for example, piles of powders, 9

crystals, splinters, any other rough surface etc.). The initiation occurs usually at or near the 10

centre of the substance or mixture pile with the available air in the interspace between the 11

particles. 12

Since the surface area of a solid substance or mixture exposed to air increases with decreasing 13

particle size, it follows that particle size and shape will greatly influence the propensity of a 14

substance or mixture to self-heat. Therefore it is very important that self-heating properties for 15

solids, and especially powders, are determined for the substance or mixture in the form it is 16

supplied and expected to be used. 17

2.11.2. Definitions and general considerations for the classification of self-18

heating substances and mixtures 19

The definitions in CLP for self-heating substances and mixtures are as follows: 20

Annex I: 2.11.1.1. A self-heating substance or mixture is a liquid or solid substance or

mixture, other than a pyrophoric liquid or solid, which, by reaction with air and without energy

supply, is liable to self-heat; this substance or mixture differs from a pyrophoric liquid or solid

in that it will ignite only when in large amounts (kilograms) and after long periods of time

(hours or days).

2.11.1.2. Self-heating of a substance or a mixture is a process where the gradual reaction of

that substance or mixture with oxygen (in the air) generates heat. If the rate of heat

production exceeds the rate of heat loss, then the temperature of the substance or mixture

will rise which, after an induction time, may lead to self-ignition and combustion.


Pyrophoric solids and liquids should not be considered for classification as self-heating 22

substances and mixtures. 23

2.11.4. Classification of self-heating substances and mixtures 24


Self-heating is a very complex phenomenon which is influenced by many parameters (some of 26

them being volume, temperature, particle shape and size, heat conductivity and bulk density). 27

Therefore, self-heating behaviour cannot be predicted from any theoretical model. In some 28

cases, properties might even differ between producers of seemingly very similar substances or 29

mixtures. Differences in self-heating behaviour are especially to be anticipated where surface 30




treatment occurs in the production process. Hence, all data sources should be carefully 1

evaluated with regard to reliability and scientific validity. 2

It is of utmost importance that in compliance with Articles 5 and 6 of CLP authentic and 3

representative material in the correct form and physical state be used for testing. In many 4

cases, a simple screening test (see Section 2.11.4.2) can be used to determine whether self-5

heating occurs or not. 6


Annex I: 2.11.4.2. The classification procedure for self-heating substances or mixtures

need not be applied if the results of a screening test can be adequately correlated with the

classification test and an appropriate safety margin is applied. Examples of screening tests

are:

(a) The Grewer Oven test (VDI guideline 2263, part 1, 1990, Test methods for the De-

termination of the Safety Characteristics of Dusts) with an onset temperature 80 K above

the reference temperature for a volume of 1 l;

(b) The Bulk Powder Screening Test (Gibson, N. Harper, D.J. Rogers, R. Evaluation of the

fire and explosion risks in drying powders, Plant Operations Progress, 4 (3), 181-189, 1985)

with an onset temperature 60 K above the reference temperature for a volume of 1 l.

EU test method A.16 as described in Regulation (EC) No 440/2008 checks for self-heating 8

properties. However, the method used is generally inappropriate for a sound assessment, and 9

the findings do not lead to a classification. Therefore, special care must be taken if results from 10

EU test method A.16 are interpreted towards a CLP classification for self-heating substances 11

and mixtures. 12

In general, the phenomenon of self-heating applies only to solids. The surface of liquids is not 13

large enough for reaction with air and the test method is not applicable to liquids. Therefore 14

liquids are not classified as self-heating. However, if liquids are adsorbed on a large surface 15

(e.g. on powder particles), a self-heating hazard should be considered. 16

Substances or mixtures with a low melting point (< 160 °C) should not be considered for 17

classification in this class since the melting process is endothermic and the substance-air 18

surface is drastically reduced. However, this criterion is only applicable if the substance or 19

mixture is completely molten up to this temperature. 20


A self-heating substance or mixture must be classified in one of the two categories for this class 22

if, in a test performed in accordance with UN Test N.4 in Part III, Sub-section 33.3.1.6 of the 23

UN-MTC, the result meets the criteria according to following table: 24


Criteria for self-heating substances and mixtures

Category Criteria

1 A positive result is obtained in a test using a 25 mm sample cube at 140 °C

2

(a) a positive result is obtained in a test using a 100 mm sample cube at 140 °C

and a negative result is obtained in a test using a 25 mm cube sample at

140 °C and the substance or mixture is to be packed in packages with a volume

of more than 3 m3; or

114



(b) a positive result is obtained in a test using a 100 mm sample cube at 140 °C

and a negative result is obtained in a test using a 25 mm cube sample at

140 °C, a positive result is obtained in a test using a 100 mm cube sample at

120 °C and the substance or mixture is to be packed in packages with a volume

of more than 450 litres; or

(c) a positive result is obtained in a test using a 100 mm sample cube at 140 °C

and a negative result is obtained in a test using a 25 mm cube sample at 140

°C and a positive result is obtained in a test using a 100 mm cube sample at

100 °C.

Note

The test shall be performed on the substance or mixture in its physical form as presented.

If, for example, for the purposes of supply or transport, the same chemical is to be presented

in a physical form different from that which was tested and which is considered likely to

materially alter its performance in a classification test, the substance shall also be tested in the

new form.

2.11.2.3. Substances and mixtures with a temperature of spontaneous combustion higher than

50 °C for a volume of 27 m³ shall not be classified as a self-heating substance or mixture.

2.11.2.4. Substances and mixtures with a spontaneous ignition temperature higher than 50 °C

for a volume of 450 litres shall not be assigned to Category 1 of this class.


A self-heating substance or mixture must be classified in one of the two categories for this class 2

using UN Test N.4 in Part III, Sub-section 33.3.1.6 of the UN-MTC. 3

2.11.4.4.1. General remarks 4

If self-heating behaviour cannot be ruled out by a screening test, further testing becomes 5

necessary. UN Test N.4 as described in the latest version of the UN-MTC should be used. 6

Explosive substances and mixtures should not be tested according to this method. For safety 7

reasons, it is advisable to test for explosive and self-reactive properties and to rule out 8

pyrophoric behaviour before performing this test. The oven should be equipped with an 9

appropriate pressure-release device in case an energetic decomposition is triggered by a 10

temperature rise. For samples containing flammable solvents explosion protection measures 11

have to be taken. 12

The tests may be performed in any order. It is suggested to start with the 25 mm sample cube 13

at 140 °C. If a positive result is obtained, the substance or mixture must be classified as a self-14

heating substance or mixture, Category 1, and no further testing is necessary. 15

The test procedure need not be applied if the substance or mixture is completely molten at 160 16

°C. 17

2.11.4.4.2. Sample preparation 18

The sample (powder or granular) in its commercial form should be used and should not be 19

milled or ground. It should be filled to the brim of the sample container and the container 20

tapped several times. If the sample settles, more is added. If the sample is heaped it should be 21

levelled to the brim. The sample container is placed in the oven as described in the UN-MTC. 22

2.11.4.4.3. Criteria and evaluation 23

A positive result is obtained if spontaneous ignition occurs or if the temperature of the sample 24

exceeds the oven temperature by 60 K. The testing time is 24 hours. The time count starts 25

when the temperature in the centre of the sample has reached a value of 2 K below the oven 26



temperature. This is especially important when the sample contains solvents which evaporate 1

under the test conditions or when larger test volumes are used for extrapolation purposes (see 2

below). 3

Before starting UN Test N.4, the decomposition behaviour of the sample should be known. In 4

general, it is sufficient to perform a screening with Differential Scanning Calorimetry. Special 5

care with respect to the interpretation of the test data is necessary when exothermic 6

decomposition may occur at the test temperatures. In such cases, a test under an inert 7

atmosphere (i.e. nitrogen) should be run to determine the temperature rise due to 8

decomposition. Careful flushing with the chosen inert gas is essential in such cases since 9

otherwise much air may be retained between the crystals of the sample in the container. 10


The following decision logic for self-heating substances and mixtures is applicable according to 12

CLP. 13

NOTE: The person responsible for the classification of self-heating substances and mixtures

should be experienced in this field and be familiar with the criteria for classification.

116



Annex I: Figure 2.11.1.

Self-heating substances and mixtures

2.11.4.6. Exemption 1

The following exemptions apply (see Section 2.11.4.3): 2

Substances and mixtures with a temperature of spontaneous combustion higher than 50 3

°C for a volume of 27 m³ must not be classified as a self-heating substance or mixture. 4

SUBSTANCE/MIXTURE

Does it undergo dangerous self-heating when

tested in a 100 mm sample cube at 140 °C? NO

NOT CLASSIFIED

YES

Does it undergo dangerous self-heating when

tested in a 25 mm sample cube at 140 °C? YES

NO

Category 1

Danger

Is it packaged in more than 3 m3?

Does it undergo dangerous self-heating when tested in a 100 mm sample cube at 120 °C?

YES

Category 2

Warning NO

NO NOT CLASSIFIED

Is it packaged in more than 450 litres volume?

NO

YES

YES

Category 2

Warning

Category 2

Warning

Does it undergo dangerous self-heating when tested in a 100 mm sample cube at 100 °C? YES

NO

NOT CLASSIFIED



Substances and mixtures with a spontaneous ignition temperature higher than 50 °C for 1

a volume of 450 litres must not be assigned to Category 1 of this class. 2

However, the UN-MTC does not provide any guidance on how these values should be 3

determined. The UN test regime is based on the assumption of a cubic sample shape. For the 4

extrapolation to larger volumes, an improved model has to be used. According to Grewer 5

(Grewer, 1994), plotting the logarithm of the volume to surface ratio (log (V/A)) versus the 6

reciprocal temperature gives good results without knowledge of the Frank-Kamenetzskii (Frank-7

Kamenetzskii, 1969) shape factor. 8

The critical temperature for a volume of 450 l or 27 m³ can be found by extrapolation of the 9

critical temperature in a log (V/A) vs. 1/T plot (see Figure 2.11.4—a): 10

Figure 2.11.4—a Extrapolation towards large volumes 11

12

The test setup is essentially the same as in UN Test N.4 of the UN-MTC but now the sample size 13

and possibly the shape are systematically varied. The criteria of section 2.11.4.3 apply as well. 14

The critical temperature must be determined over a range of at least four different volumes and 15

with a volume not smaller than 16 ml. If possible, larger volumes should be also tested. The 16

borderline temperature should be determined as precisely as possible. For small volumes (< 1 17

litre), the temperature rise due to self-heating may be considerably less than 60 K; in this case 18

a noticeable temperature rise is interpreted as a positive result. 19

A conservative approach is required for the evaluation. The uncertainty of measurement must 20

be taken into account. The extrapolation must be based on a linear regression of the negative 21

and positive borderline data sets in the log (V/A) vs. 1/T diagram. The maximum permissible 22

difference between a positive and a negative result should be 5 K. An exemption may be 23

claimed if the more conservative endpoint for the particular volume is well beyond 50 °C (i.e. 24

55 °C or higher). 25

400 mL

100 L

5060708090100120140160180200220240

1,6 L

110 mL

16 mL

1 m3

10 m3

27 m3

-3,0

-2,8

-2,6

-2,4

-2,2

-2,0

-1,8

-1,6

-1,4

-1,2

-1,0

-0,8

-0,6

-0,4

0,0019 0,0020 0,0021 0,0022 0,0023 0,0024 0,0025 0,0026 0,0027 0,0028 0,0029 0,0030 0,0031

log

(V/A

) in

m

Temperature in °C

Sa

mp

le v

olu

me

reciprocal abs. Temperature in 1/K

positive result

negative result

Note: sample gave positive

result at 140 °C / 1 liter

Linear regression lines

Extrapolation to 27 m³

118



2.11.5. Hazard communication for self-heating substances and mixtures 1


statements 3


Label elements for self-heating substances and mixtures

Classification Category 1 Category 2

GHS Pictograms

Signal Word Danger Warning

Hazard Statement H251: Self-heating; may

catch fire

H252: Self-heating in large

quantities; may catch fire

Precautionary Statement

Prevention

P235

P280

P235

P280

Precautionary Statement Response


P407

P413

P420

P407

P413

P420




Division 4.2 – substances and mixtures liable to spontaneous combustion – within Class 4 of the 6

UN RTDG Model Regulations comprises the following entries: 7

a. pyrophoric substances and mixtures ; 8

b. self-heating substances and mixtures. 9

Whereas pyrophoric substances and mixtures in the modal transport regulations (ADR, RID, 10

ADN and IMDG Code, ICAO TI) are assigned to packing group I, self-heating substances and 11

mixtures are assigned to packing groups II and III. In cases where a substance or mixture is 12

classified in Division 4.2, packing group II or III, the translation into the CLP system is 13

straightforward. 14

It should be kept in mind that transport classification is based on prioritisation of hazards (see 15

UN RTDG Model Regulations, Section 2.0.3) and that self-heating substances and mixtures have 16

a relatively low rank in the precedence of hazards. Therefore, the translation from the modal 17

transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) to CLP should be only done if a 18

transport classification as self-heating is explicitly available. The conclusion that a substance or 19

mixture not classified as self-heating for transport should not be classified as a self-heating 20



substance or mixture according to CLP is, in general, not correct. See Annex VII for additional 1

information on transport classification in relation to CLP classification. 2

2.11.7. Examples of classification for self-heating substances and mixtures 3


criteria 5

many organometallic compounds, especially substances or mixtures containing transition 6

metals; 7

many organic substances or mixtures; the tendency to self-heat increases with 8

decreasing particle size; 9

many metals, especially catalysts. 10



In general, liquids show no self-heating behaviour unless adsorbed on a large surface. 13

Scientific background 14

A basic model for the thermal explosion of solids was first developed by Frank-Kamenetzskii 15

(Frank-Kamenetzskii, 1969). It is based on the assumption that only the heat loss by thermal 16

conduction is relevant for the phenomenon. In this case, the critical criterion for a thermal 17

runaway reaction can be described as a linear relationship between the reciprocal absolute 18

temperature and the logarithm of volume. 19

The classification scheme of the UN for self-heating substances and mixtures is based on 20

charcoal as a reference system. The critical temperature for a 1 litre cube of charcoal is 140 °C 21

and for a cube of 27 m³ 50 °C. When a parallel line is drawn in the 1/T vs. logarithm of volume 22

diagram from the reference points 1 litre / 120 °C and 1 litre / 100 °C, the corresponding 23

volumes for a critical temperature of 50 °C are found to be 3 m³ and 450 l, respectively (see 24

Figure 2.11.7—a). The black dotted line in Figure 2.11.7—a separates Category 1 from Category 25

2. For examples of results following the Test N.2 see Section 33.3.1.4.5 of UN-MTC. 26

However, the slope of the line in the 1/T vs. volume diagram depends on the individual 27

activation energy of the substance or mixture, and therefore it may vary within certain limits. It 28

must be born in mind that this test regime has been developed to facilitate classification and 29

that it may not suffice to solve safety issues in storage. 30

120



Figure 2.11.7—a Volume dependency of the critical temperature for charcoal 1

2

3

4


Grewer, T. (1994). Thermal hazards of chemical reactions, Elsevier. 6

Frank-Kamenetzskii, D.A. (1969). Diffusion and heat transfer in chemical kinetics, 2nd edition, 7

Plenum Press, New York, London. 8

9

0,002

0,0022

0,0024

0,0026

0,0028

0,003

0,0032

0,001 0,01 0,1 1 10 100 1000 10000 100000

Te

mp

era

ture

(°C

)

50

60

70

80

90

100

120

140

160

180

200

220

Volume (liter)

recipr.

Temp.

Charcoal reference line

(UN Manual T + C)

Not self-heating

Exemption < 3 m³

Exemption < 450 ltr

Cat. 1

Cat. 2

Yellow dots symbolize

UN Manual test points

Grewer test



2.12. SUBSTANCES AND MIXTURES WHICH, IN CONTACT WITH WATER, 1

EMIT FLAMMABLE GASES 2


The criteria for ‘Substances and mixtures which, in contact with water, emit flammable gases’ 4

are found in Annex I, Section 2.12 of CLP and are identical to those in Chapter 2.12 of GHS15. 5

Depending on the chemical structure and/or the physical state (e.g. particle size) substances or 6

mixtures may be able to react with water (even damp / air humidity) under normal ambient 7

temperature conditions. Sometimes this reaction can be violent and/or with significant 8

generation of heat. Especially if gases are evolved this reaction may become very dangerous 9

during use. In addition, it is important to know whether a substance or mixture emits 10

flammable gases after contact with water because special precautions are necessary especially 11

with regard to explosion protection. 12

Examples are demonstrated in the following table. 13

Table 2.12.1—a Examples of hazards, depending on the property of the emitted gas, when 14 substances and mixtures are in contact with water 15

Type of emitted gas

Example of the hazard CLP Reference

Gas (in general)

Heating up of the substance

Splashing of the substance and thus e.g. contact with skin etc. or additional risk during fire fighting

Pressure rise and bursting of e.g. the packaging, tank

Annex II, 1.1.3: Supplemental hazard information:

EUH014*

Flammable gas Ignition

Flash of fire

Annex I, 2.12: H260/H261

Toxic gas Damage to health: intoxication (acute) Annex II, 1.2.1: Supplemental hazard information:

EUH029

* For supplemental hazard information: see Section 2.12.4.2 16


substances and mixtures which, in contact with water, emit flammable 18

gases 19

The following definition is given in CLP for substances and mixtures which, in contact with 20

water, emit flammable gases (CLP Annex I, 2.12). 21


122



Annex I: 2.12.1. Substances or mixtures which, in contact with water, emit flammable gases

means solid or liquid substances or mixtures which, by interaction with water, are liable to

become spontaneously flammable or to give off flammable gases in dangerous quantities.


If the chemical identity of the emitted gas is unknown, the gas must be tested for flammability 2

(unless it ignites spontaneously). Other than under DSD/DPD, pyrophporic liquids and 3

pyrophoric solids have to be considered for classification in this hazard class as well and data 4

about pyrophoric properties are needed prior to testing for this hazard class. 5

2.12.4. Classification of substances and mixtures which, in contact with 6

water, emit flammable gases 7


For the classification of substances and mixtures which, in contact with water, emit flammable 9

gases the following data are needed, if applicable: 10

chemical structure; 11

water solubility; 12

chemical identity and flammability of the emitted gas; 13

pyrophoric properties of the tested substance or mixture; 14

particle size in case of solids; 15

friability in case of solids; 16

hazard properties in general; 17

information concerning the experience in production or handling. 18

See also IR & CSA, Chapter R.7a: Endpoint specific guidance, Section R.7.1.7 (Water solubility), 19

R.7.1.14 (Granulometry). 20

Information about the chemical structure is used to check whether the substance or mixture 21

contains metals and/or metalloids. 22

The water solubility is used to decide whether the substance or mixture is soluble in water to 23

form a stable mixture. This may also be decided based on information concerning experience in 24

handling or use, e.g. the substance or mixture is manufactured with water or washed with 25

water (see Section 2.12.4.4.1). 26

The chemical identity of the emitted gas is used to decide whether the evolved gas is flammable 27

or not. If the chemical identity of the emitted gas is unknown, the gas must be tested for 28

flammability (see Section 0). 29

In case of pyrophoric substances and mixtures the UN Test N.5 of the UN-MTC, Part III, Section 30

33.4.1.3.1 must be executed under nitrogen atmosphere. Therefore, data about pyrophoric 31

properties are needed prior to testing. 32

The melting point, boiling point and information about viscosity are necessary to identify the 33

physical state of the substance or mixture. See also IR & CSA, Chapter R.7a: Endpoint specific 34

guidance, Section R.7.1.2 (Melting point/freezing point), R.7.1.3 (Boiling point), R.7.1.18 35

(Viscosity). 36



Even though the UN Test N.5 can be applied to both, solids and liquids, these data are 1

necessary to decide whether information concerning the friability (for solids) in accordance with 2

the test method is necessary. 3

The particle size and the friability of a solid substance or mixture are crucial parameters for the 4

classification of substances and mixtures which, in contact with water, emit flammable gases. 5

These parameters have a significant effect on the test result. Thus specific requirements 6

regarding the particle size and the friability are prescribed in the UN Test N.5. For further details 7

regarding the test procedure see Section 2.12.4.4.1. 8

The references in Section 2.12.8 provide good quality data on physical hazards. 9


For the majority of substances and mixtures, flammability as a result of contact with water is 11

not a typical property and testing can be waived based on a consideration of the structure and 12

experiences in handling and use. 13

Annex I: 2.12.4.1. The classification procedure for this class need not be applied if:

a) the chemical structure of the substance or mixture does not contain metals or metalloids;

or

b) experience in handling and use shows that the substance or mixture does not react with

water, e.g. the substance is manufactured with water or washed with water; or

c) the substance or mixture is known to be soluble in water to form a stable mixture.



Criteria for substances or mixtures which in contact with water emit flammable gas

Category Criteria

1

Any substance or mixture which reacts vigorously with water at ambient

temperatures and demonstrates generally a tendency for the gas produced to

ignite spontaneously, or which reacts readily with water at ambient temperatures

such that the rate of evolution of flammable gas is equal to or greater than 10

litres per kilogram of substance over any one minute.

2

Any substance or mixture which reacts readily with water at ambient temperatures

such that the maximum rate of evolution of flammable gas is equal to or greater

than 20 litres per kilogram of substance per hour, and which does not meet the

criteria for Category 1.

3

Any substance or mixture which reacts slowly with water at ambient temperatures

such that the maximum rate of evolution of flammable gas is equal to or greater

than 1 litre per kilogram of substance per hour, and which does not meet the

criteria for Categories 1 and 2.

Note:

The test shall be performed on the substance or mixture in its physical form as presented. If

for example, for the purposes of supply or transport, the same chemical is to be presented in

a physical form different from that which was tested and which is considered likely to

124



materially alter its performance in a classification test, the substance must also be tested in

the new form.

2.12.2.2. A substance or mixture shall be classified as a substance or mixture which in

contact with water emits flammable gases if spontaneous ignition takes place in any step of

the test procedure.


2.12.4.4.1. Testing procedure 2

Care must be taken during testing as the emitted gas might be toxic or corrosive. 3

The testing procedure for substances and mixtures which in contact with water emit flammable 4

gases is sensitive to a number of influencing factors and therefore must be carried out by 5

experienced personnel. Some of these factors are described in the following: 6

2. Apparatus / measuring technique 7

In UN Test N.5 no special laboratory apparatus / measuring technique to determine the rate of 8

gas evolution is required and no reference material is prescribed. As demonstrated in the past 9

by a round robin test (Kunath, K. et al. 2011), the gas evolution rate measured by different 10

apparatuses may vary widely. Therefore in order to avoid measuring and classification errors 11

adequate quality control measures are necessary to validate the results and should be noted in 12

the test report. 13

3. Particle size and/or friability 14

The particle size of a solid has a significant effect on the test result. Therefore, if for solids the 15

percentage of powder with a particle size of less than 500 µm constitutes more than 1 % of the 16

total mass, or if the substance or mixture is friable, then the complete sample must be ground 17

to a powder before testing to account for a possible reduction in particle size during handling 18

and transport. 19

In certain cases, grinding may not be applicable and/or the sample cannot be ground 20

completely to a particle size of less than 500 µm (e.g. metal granules). 21

Information on these pre-treatments and the respective procedures, the particle size and the 22

friability has to be provided in the test report. 23

4. Atmospheric parameters 24

Variations of the atmospheric parameters (mainly air pressure and temperature) during the test 25

have a considerable influence on the test result. Therefore the substance or mixture must be 26

tested at 20 °C, i.e. make sure that the test apparatus is acclimatised to 20 °C. 27

On the other hand it is difficult to regulate and stabilise the air pressure during the testing. To 28

characterise this influencing factor and to avoid false positive results, an additional ‘blank test’ 29

is highly recommended. The results of the blank test should be noted in the test report. 30

5. Test with demineralised (distilled) water 31

The UN Test N.5 is performed with demineralised (distilled) water. In practice, contact with 32

water can be to water in the liquid state (fresh water, sea water) or humid air, respectively. 33

Note that the reactivity and thus the gas evolution rate observed in practice may differ from the 34

gas evolution rate value measured using demineralised water. This should be taken into account 35

when handling substances and mixtures which in contact with water emit flammable gases. 36

6. Stirring procedures during the test 37

Stirring of the sample or water mixture during the test may have a considerable effect on the 38

test result (e.g. significant increase or decrease of the gas evolution rate). Therefore, the 39



sample or water mixture should not be stirred continuously during the test, e.g. by an 1

automatic magnetic stirrer, even if the test sample has hydrophobic properties and moistening 2

of the sample becomes impossible (see Kunath K. et al., 2011). 3

7. Spontaneous ignition 4

Spontaneous ignition of the evolved gas without contact with an additional ignition source, i.e. 5

without the flame of the gas burner results in classification as Category 1. This does not 6

necessarily mean that the evolved gas is pyrophoric but often the heat of reaction is sufficient 7

to ignite the evolved gas (e.g. the hydrogen evolved when sodium reacts with water). 8

2.12.4.4.2. Evaluation of hazard information 9

In order to accurately interpret the test results the evaluating person must have sufficient 10

experience in the application of the test methods and in the disturbing / influencing factors as 11

described above. 12

The evaluation of data comprises two steps: 13

evaluation of all available data; and 14

identification of the study or studies giving rise to the highest concern (key studies). 15

The criteria for assignment to Category 2 or 3 are gas evolution rates of 20 and 1 litre per 16

kilogram of substance or mixture per hour, respectively, but for Category 1 the relevant 17

criterion is 10 litres per kilogram of substance or mixture over any one minute period (if the gas 18

does not ignite spontaneously). This has to be considered while testing and for correct 19

evaluation of the test results. 20

The assignment to the respective hazard class/category will further determine the technical 21

means to be taken to avoid dangerous events which, in combination with other safety 22

characteristics such as i) explosion limits, ii) flash points (applicable only for liquids) or iii) self-23

ignition temperature, can lead to clear restrictions in the conditions of use. 24


Classification of substances and mixtures which, in contact with water, emit flammable gases is 26

done according to decision logic 2.12.4.1 as included in the GHS. 27

NOTE: The person responsible for the classification of substances and mixtures which, in

contact with water, emit flammable gases should be experienced in this field and be familiar

with the criteria for classification.

126



Figure 2.12.4—a Decision logic for substances and mixtures which, in contact with water, emit 1 flammable gases (Decision logic 2.12 of GHS) 2

3

In contact with water, does it react slowly at ambient temperatures such that the maximum rate of evolution of flammable gas is ≥ 1 litre per kg

of substance per hour?

In contact with water, does the substance react vigorously with water at ambient temperatures and demonstrate generally a tendency for the gas

produced to ignite spontaneously, or does it react readily with water at ambient temperatures such that the rate of evolution of flammable gas is

≥ 10 litres per kg of substance over any one minute?

Not classified

Category 1

Danger

Substance/mixture

In contact with water, does it react readily with water at ambient temperatures such that the maximum rate of evolution of flammable

gas is ≥ 20 litres per kg of substance per hour?

Category 2

Danger

Category 3

Warning

Yes

Yes

Yes

No

No

No



2.12.5. Hazard communication for substances and mixtures which, in contact 1

with water, emit flammable gases 2


statements for substances and mixtures 4


Label elements for substances or mixtures which in contact with water emit

flammable gases


GHS Pictograms


Hazard Statement H260:

In contact with water

releases flammable

gases which may

ignite spontaneously

H261:

In contact with

water releases

flammable gases

H261:

In contact with

water releases

flammable gases

Precautionary

Statement

Prevention

P223

P231 + P232

P280

P223

P231 + P232

P280

P231 + P232

P280

Precautionary

Statement Response

P302 + P335 + P334

P370 + P378

P302 + P335 +

P334

P370 + P378

P370 + P378

Precautionary

Statement Storage

P402 + P404 P402 + P404 P402 + P404

Precautionary

Statement Disposal

P501 P501 P501



Annex II of CLP provides the following additional labelling provisions for water-reactive 7

substances and mixtures. These statements must be assigned in accordance with CLP, Article 8

25 (1), to substances and mixtures classified for physical, health or environmental hazards. 9

There are no criteria or test methods provided for these EUH statements. 10

11

128



Annex II: 1.1.3. EUH014 – 'Reacts violently with water'

For substances and mixtures which react violently with water, such as acetyl chloride, alkali

metals, titanium tetrachloride.

Annex II: 1.2.1. EUH029 - 'Contact with water liberates toxic gas'

For substances and mixtures which in contact with water or damp air, evolve gases classified

for acute toxicity in category 1, 2 or 3 in potentially dangerous amounts, such as aluminium

phosphide, phosphorus pentasulphide.


Division 4.3 within Class 4 of the UN RTDG Model Regulations covers substances and mixtures 2

which in contact with water emit flammable gasses. Substances and mixtures which are 3

classified and/or labelled in Division 4.3 in the modal transport regulations (ADR, RID, ADN and 4

IMDG Code, ICAO TI) are classified as substances and mixtures which, in contact with water, 5

emit flammable gases under CLP. See Annex VII for additional information on transport 6


2.12.7. Examples of classification for substances and mixtures which, in 8

contact with water, emit flammable gases 9

2.12.7.1. Example of a substance fulfilling the classification criteria 10

Many different types of chemicals may belong to the hazard class of substances and mixtures 11

which, in contact with water, emit flammable gases, for example, alkali metals, alkyl aluminium 12

derivatives, alkyl metals, metal hydrides, metal phosphides, certain metal powders. A 13

comprehensive list can be found in Bretherick’s Handbook of Reactive Chemical Hazards (Urben, 14

2007). 15

2.12.7.1.1. Example 1 16

Pyrophoric substance fulfilling the criteria for CLP classification

Substance: Magnesium alkyls (Index No. 012-003-00-4)

Chemical structure: R2Mg

Flammable gas: Hydrogen

Gas evolution rate: not applicable

Spontaneous ignition: not possible due to the nitrogen atmosphere during the UN Test N.5

DSD classification: F; R14-17

Transport classification: -

Reference: Former Annex I to DSD and Annex VI to CLP

CLP Classification: Water-react. 1; H260

Pyr. Sol. 1; H250



Supplemental Hazard Information: EUH014

1

130



2.12.7.2. Example of a substance not fulfilling the classification criteria 1

2.12.7.2.1. Example 2 2

Manganese ethylene bis (dithiocarbamate) complex with zinc salt 88 % (Mancozeb)

Gas evolution rate: 0 litres per kilogram of substance per hour.

Spontaneous ignition: not applicable

Transport classification: not Class 4.3

Reference: UN Test N.5, UN-MTC Table 33.4.1.4.5

CLP Classification: Not classified as substance which, in contact with

water, emit flammable gases


William M. Haynes et al. (2012) CRC Handbook of Chemistry and Physics 93rd Edition. CRC 4

Press, Taylor and Francis, Boca Raton, FL 5

GESTIS-database on hazardous substances: 6

http://www.dguv.de/bgia/en/gestis/stoffdb/index.jsp 7

O'Neil, Maryadele J. et al. (2016, 2012) The Merck Index - An Encyclopaedia of Chemicals, 8

Drugs, and Biologicals (14th Edition – Version 14.9). Merck Sharp & Dohme Corp., a subsidiary 9

of Merck & Co., Inc. 10



Kunath, K., Lüth, P., Uhlig, S. (2011). Interlaboratory test on the method UN Test N.5 / EC A.12 13

“Substances which, in contact with water, emit flammable gases” 2007.Short report. BAM 14

Bundesanstalt für Materialforschung und –prüfung. Berlin. ISBN 978-3-9814634-1-5. 15

http://www.bam.de/de/service/publikationen/publikationen_medien/short__report_rv_un_n_5.16

pdf 17

18

http://www.dguv.de/bgia/en/gestis/stoffdb/index.jsp

http://www.bam.de/de/service/publikationen/publikationen_medien/short__report_rv_un_n_5.pdf

http://www.bam.de/de/service/publikationen/publikationen_medien/short__report_rv_un_n_5.pdf



2.13. OXIDISING LIQUIDS 1


The criteria for ‘Oxidising liquids’ are found in Annex I, Section 2.13 of CLP and are identical to 3


The hazard class oxidising liquids comprises liquid substances and mixtures whose hazard is 5

characterised by the fact that, in contact with other materials, they are able to cause or 6

contribute to the combustion of those materials. The other materials do not necessarily have to 7

belong to a certain hazard class in order to be able to be affected by the presence of oxidising 8

substances or mixtures. This is for example the case when a solid material (e.g. wood) is 9

soaked with an oxidising liquid. 10

Certain combinations of combustible materials and oxidising substances or mixtures may even 11

result in spontaneous combustion, thermal instability or form an explosive mixture, this means 12

that they may have explosive properties or may be regarded as self-reactive substances or 13

mixtures. 14

Although widely known as oxidising materials, their hazard and behaviour might be better 15

understood by considering them to be fire enhancing substances or mixtures. 16

The hazards communication of oxidising liquids intends to communicate the property that it may 17

cause fire or explosion or that it may intensify fire. 18

Apart from the combustion hazard, the production of toxic and/or irritating fumes may cause an 19

additional hazard. For example, when nitrates are involved in a fire, nitrous fumes may be 20

formed. 21

The testing procedure and criteria for oxidising substances or mixtures do not work properly for 22

ammonium nitrate compounds or solutions, ammonium nitrate based fertilizers and ammonium 23

nitrate emulsions, suspensions or gels. Therefore for classification and labelling of substances or 24

mixtures containing ammonium nitrate, known experience should be used and expert 25

judgement should be sought. For the classification procedures for ammonium nitrate emulsions, 26

suspensions or gels – intermediate for blasting explosives, see Chapter 2.1 of this guidance. 27

Annex I: 2.13.4.3

In the event of divergence between test results and known experience in the handling and

use of substances or mixtures which shows them to be oxidising, judgments based on known

experience shall take precedence over test results.


oxidising liquids 29

The CLP text comprises the following definition for oxidising liquids. 30


Oxidising liquid means a liquid substance or mixture which, while in itself not necessarily

combustible, may, generally by yielding oxygen, cause, or contribute to, the combustion of

other material.


132




Oxidising liquids that are mixed with combustible materials or reducing agents may have 2

explosive properties and should be considered for classification in the hazard class Explosives 3

(including the applicable screening procedures), see Chapter 2.1 of this guidance. 4

In rare cases, mixtures with oxidising liquids may exhibit self-reactive behaviour, see Chapter 5

2.8 of this guidance. Expert judgement should be sought in case of doubt. 6

The classification procedure and criteria for oxidising substances or mixtures is not applicable 7

for organic peroxides. Under DSD organic peroxides were considered to be oxidising substances 8

or mixtures because of the presence of the –O–O– bond. The majority of the organic peroxides 9

do not possess oxidising properties; their main hazards are reactivity and flammability. Under 10

CLP organic peroxides are comprised in a separate hazard class (CLP Annex I, 2.15) and they 11

must not be considered according to the procedures described for oxidising liquids. Organic 12

peroxides were classified as oxidising (O; R7) according to the DSD, which was not appropriate 13

since the vast majority of them do not exhibit oxidising properties. 14

Inorganic oxidising liquids are not flammable and therefore do not have to be subjected to the 15

classification procedures for the hazard classes flammable liquids or pyrophoric liquids. Also 16

other liquids that are classified as oxidising liquids are normally not flammable, although a few 17

exemptions may exist. Expert judgement should be sought in case of doubt. 18

2.13.4. Classification of substances and mixtures as oxidising liquids 19


Oxidising liquids may cause, or contribute to, the combustion of other material. Although the 21

definition states that they generally do this by yielding oxygen, halogens can behave in a similar 22

way. Therefore, any substance or mixture containing oxygen and/or halogen atoms should in 23

principle be considered for inclusion into the hazard class oxidising liquids. This does not 24

necessarily mean that every substance or mixture containing oxygen and/or halogen atoms 25

should be subjected to the full testing procedure. 26

2.13.4.1.1. Screening procedures and waiving of testing 27

Liquids that are classified as explosives should not be subjected to the testing procedures for 28

oxidising liquids. 29

Organic peroxides should be considered for classification within the hazard class organic 30

peroxides, see Chapter 2.15 of this guidance. 31

Experience in the handling and use of substances or mixtures which shows them to be oxidising 32

is an important additional factor in considering classification as oxidising liquids. In the event of 33

divergence between test results and known experience, judgement based on known experience 34

should take precedence over test results. 35

Before submitting a substance or a mixture to the full test procedure, an evaluation of its 36

chemical structure may be very useful as it may prevent unnecessary testing. The person 37

applying this procedure should have sufficient experience in testing and in theoretical evaluation 38

of hazardous substances and mixtures. The following text provides a guideline for the 39

theoretical evaluation of potential oxidising properties on basis of its composition and chemical 40

structure. In case of doubt, the full test must be performed. 41

For organic substances or mixtures the classification procedure for this hazard class need not to 42

be applied if: 43

a. the substance or mixture does not contain oxygen, fluorine or chlorine; or 44



b. the substance or mixture contains oxygen, fluorine or chlorine and these elements 1

are chemically bonded only to carbon or hydrogen. 2

For inorganic substances or mixtures, the classification procedure for this hazard class need not 3

be applied if they do not contain oxygen or halogen. 4

On basis of this theoretical evaluation only a distinction can be made between ‘potentially 5

oxidising’ (i.e. further testing required) and ‘non-oxidising’ (i.e. no further testing for this 6

hazard class required). It is not possible to assign a hazard category on basis of a theoretical 7

evaluation. 8

Any substance or mixture that complies with the above waiving criteria can be safely regarded 9

to have no oxidising properties and, hence, needs not to be tested and needs not to be 10

regarded as an oxidising liquid. However, such a substance or mixture may still possess other 11

hazardous properties that require classification into another hazard class. 12

In case a mixture of an oxidising substance and a non-hazardous inert substance is offered for 13

classification, the following should be taken into account: 14

An inert material by definition does not contribute to the oxidising capability of the 15

oxidising substance. Hence, the mixture can never be classified into a more severe 16

hazard category. 17

If an oxidising substance is mixed with an inert material, the oxidising capability of the 18

mixture does not linearly decrease with decreasing content of oxidising substance. The 19

relationship is more or less logarithmic and depends on the characteristics of the 20

oxidising substance. For instance, a mixture containing 50 % of a strong oxidiser and 50 21

% of an inert material may retain 90 % of the oxidising capability of the original 22

oxidising component. Non-testing classification of mixtures based solely on test data for 23

the original oxidising substance should therefore be done with extreme care and only, if 24

sufficient experience in testing exists. 25

The determination of the oxidising properties of an aqueous solution of solid oxidising 26

substances and the classification as an oxidising mixture is not necessary provided that 27

the total concentration of all solid oxidisers in the aqueous solution is less than or equal 28

to 20 % (w/w). 29


The testing procedures for oxidising liquids are based on the capability of an oxidising liquid to 31

enhance the combustion of a combustible material. Therefore, substances and mixtures that are 32

submitted for classification testing are mixed with a combustible material. In principle, dried 33

fibrous cellulose is used as a combustible material. The mixture of the potentially oxidising 34

liquid and cellulose is then ignited and its behaviour is observed and compared to the behaviour 35

of reference materials. 36

For liquids the mixture with cellulose is ignited under confinement in an autoclave and the 37

pressure rise rate that is caused by the ignition and the subsequent reaction is recorded. The 38

pressure rise rate is compared to that of three reference material mixtures. The higher the 39

pressure rise rate, the stronger the oxidising capability of the liquid tested. 40

41

Annex I: 2.13.2.1.

An oxidising liquid shall be classified in one of the three categories for this class using test

O.2 in Part III, sub-section 34.4.2 of the UN RTDG, Manual of Tests and Criteria in

accordance with Table 2.13.1:

Table 2.13.1

134



Criteria for oxidising liquids

Category Criteria

1

Any substance or mixture which, in the 1:1 mixture, by mass, of substance (or

mixture) and cellulose tested, spontaneously ignites; or the mean pressure

rise time of a 1:1 mixture, by mass, of substance (or mixture) and cellulose is

less than that of a 1:1 mixture, by mass, of 50 % perchloric acid and cellulose.

2


mixture) and cellulose tested, exhibits a mean pressure rise time less than or

equal to the mean pressure rise time of a 1:1 mixture, by mass, of 40 %

aqueous sodium chlorate solution and cellulose; and the criteria for Category 1

are not met.

3


mixture) and cellulose tested, exhibits a mean pressure rise time less than or

equal to the mean pressure rise time of a 1:1 mixture, by mass, of 65 %

aqueous nitric acid and cellulose; and the criteria for Category 1 and 2 are not

met.

For additional information regarding the use of non-testing data see Section 2.13.4.3 below and 1

Urben, 2007 (see Section 2.13.7). 2


The test methods for oxidising liquids are designed to give a final decision regarding their 4

classification. Apart from testing, also experience in the handling and use of substances or 5

mixtures which shows them to be oxidising is an important additional factor in considering 6

classification in this hazard class. In the event of divergence between test results and known 7

experience, judgement based on known experience should take precedence over test results. 8

However, a substance or mixture must not be classified into a less severe Category based on 9

experience only. 10


Classification of oxidising liquids is done according to decision logic 2.13 as included in the GHS. 12

NOTE: The person responsible for the classification of oxidising liquids should be




Figure 2.13.4—a Decision logic for oxidising liquids (Decision logic 2.13 of GHS) 1

2

The substance/mixtures is a liquid

Does it, in the 1:1 mixture, by mass, of substance (or mixture) and cellulose tested, exhibits a pressure rise ≥ 2070 kPa (gauge)?

Does it, in the 1:1 mixture, by mass, of substance (or mixture)

and cellulose tested, exhibit a mean pressure rise time less than or

equal to the mean pressure rise time of a 1:1 mixture, by mass, of

65 % aqueous nitric acid and cellulose?


and cellulose tested, exhibit a mean pressure rise time less than or

equal to the mean pressure rise time of a 1:1 mixture, by mass, of

40 % aqueous sodium chlorate and cellulose?


and cellulose tested, spontaneously ignite or exhibit a mean

pressure rise time less than that of a 1:1 mixture, by mass, of 50 % perchloric acid and cellulose?

Category 1

Danger

Category 2

Warning

Category 3

Warning

Not classified

Not

classified

Yes

Yes

Yes

Yes

No

No

No

No

136



2.13.4.5. Hazard communication for oxidising liquids 1

2.13.4.5.1. Pictograms, signal words, hazard statements and precautionary 2

statements 3

The pictograms and hazard statements are designed to indicate that oxidising substances and 4

mixtures may cause or contribute to fire or explosion and therefore in principle should be 5

separated from combustible materials. 6

Annex I : Table 2.13.2

Label elements for oxidising liquids

Category 1 Category 2 Category 3

GHS Pictograms


Hazard Statement H271: May cause fire or

explosion; strong oxidiser

H272: May intensify

fire; oxidiser

H272: May intensify

fire; oxidiser

Precautionary

Statement

Prevention

P210

P220

P280

P283

P210

P220

P280

P210

P220

P280

Precautionary

Statement

Response

P306 + P360

P371 + P380 + P375

P370 + P378

P370 + P378 P370 + P378

Precautionary

Statement

Storage

Precautionary

Statement

Disposal

P501 P501 P501



Division 5.1 within Class 5 of the UN RTDG Model Regulations covers oxidising liquids and 9

oxidising solids, using the same tests and criteria as the CLP. Therefore, a liquid substance or 10

mixture classified as Division 5.1 (sometimes referred to as Class 5.1) according to any of the 11

modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) is normally also 12

classified as an oxidising liquid according to the CLP. Packing Groups I, II and III of the 13

transport regulations correspond directly to Categories 1, 2 and 3 of the CLP, respectively. See 14

Annex VII for additional information on transport classification in relation to CLP classification. 15



2.13.6. Examples of classification for oxidising liquids 1


criteria 3

The list of substances and mixtures fulfilling the criteria for classification is only presented for 4

information purposes. This list is not exhaustive. For examples of results see Section 34.4.2.5 of 5

UN-MTC. 6

Ferric nitrate, saturated aqueous solution 7

Lithium perchlorate, saturated aqueous solution 8

Magnesium perchlorate, saturated aqueous solution 9

Perchloric acid, 55 % 10

Sodium nitrate, 45 % aqueous solution 11



Nickel nitrate, saturated aqueous solution 14

Potassium nitrate, 30 % aqueous solution 15

Silver nitrate, saturated aqueous solution 16

2.13.7. Reference 17



20

138



2.14. OXIDISING SOLIDS 1


The criteria for ‘Oxidising solids’ are found in Annex I, Section 2.14 of CLP and are identical to 3


The hazard class oxidising solids comprises substances and mixtures whose hazard is 5

characterised by the fact that, in contact with other materials, they are able to cause or 6

contribute to the combustion of those materials. The other materials do not necessarily have to 7

belong to a certain hazard class in order to be affected by the presence of an oxidising solid. 8

This is for example the case when a liquid fuel (e.g. gas oil) mixes with an oxidising solid. 9

Certain combinations of combustible materials and oxidising substances or mixtures may even 10

result in spontaneous combustion, thermal instability or form an explosive mixture, this means 11

that they may have explosive properties or may be regarded as self-reactive substances or 12

mixtures. 13

Although widely known as ‘oxidising materials’, their hazard and behaviour might be better 14

understood by considering them to be ‘fire enhancing substances’. 15

The hazards communication of oxidising solids intends to communicate the property that it may 16

cause fire or explosion or that it may intensify fire. 17

Apart from the combustion hazard, the production of toxic and/or irritating fumes may cause an 18

additional hazard. For example, when nitrates are involved in a fire, nitrous fumes may be 19

formed. 20

The testing procedure and criteria for oxidising substances or mixtures do not work properly for 21

ammonium nitrate, ammonium nitrate compounds, ammonium nitrate based fertilizers and 22

ammonium nitrate gels. Therefore, for classification and labelling of substances and mixtures 23

containing ammonium nitrate, known experience should be used and expert judgement should 24

be sought. For the classification procedures for ammonium nitrate gels – intermediate for 25

blasting explosives, see Section 2.1 of this guidance. 26

Annex I: 2.14.4.3

In the event of divergence between test results and known experience in the handling and

use of substances or mixtures which shows them to be oxidising, judgments based on known

experience shall take precedence over test results.


oxidising solids 28

The CLP text comprises the following definition for oxidising solids. 29


Oxidising solid means a solid substance or mixture which, while in itself is not necessarily

combustible, may, generally by yielding oxygen, cause, or contribute to, the combustion of

other material.

30





The oxidising properties of a solid depend on its particle size. Smaller particles enable a more 1

intimate contact between the solid oxidiser and a combustible solid. The smaller the particle 2

size, the higher the oxidising capability of the solid. As a consequence, it may happen that large 3

particles of a certain solid are considered to be non-hazardous, while small particles of the same 4

solid need to be classified into the hazard class of oxidising solids. 5

Hence it is very important that oxidising properties for solids are investigated on the substance 6

or mixture as it is actually presented (including how it can reasonably be expected to be used, 7

see Article 8 (6) of CLP). This is indicated by the Note 2 cited in CLP Annex I, 2.14.2.1. 8

Annex I: 2.14.2.1.

[…]

Note 2: The test shall be performed on the substance or mixture in its physical form as

presented. If for example, for the purposes of supply or transport, the same chemical is to

be presented in a physical form different from that which was tested and which is considered

likely to materially alter its performance in a classification test, the substance shall also be

tested in the new form.


Oxidising solids that are mixed with combustible materials or reducing agents may have 10

explosive properties and should be considered for classification in the hazard class Explosives 11

(including the applicable screening procedures), see Chapter 2.1 of this guidance. 12

In rare cases, mixtures with oxidising solids may exhibit self-reactive behaviour, see Chapter 13

2.8 of this guidance. Expert judgement should be sought in case of doubt. 14

The classification procedure and criteria for oxidising substances and mixtures is not applicable 15

for organic peroxides. Under DSD organic peroxides were considered to be oxidising substances 16

because of the presence of the –O–O– bond. The majority of the organic peroxides do not 17

possess oxidising properties; their main hazards are reactivity and flammability. Under CLP 18

organic peroxides are comprised in a separate hazard class (CLP Annex I, 2.15) and they must 19

not be considered according to the procedures described for oxidising solids. Organic peroxides 20

were classified as oxidising (O; R7) according to the DSD, which was not appropriate since the 21

vast majority of them do not exhibit oxidising properties. 22

Inorganic oxidising solids are not flammable and therefore do not need to be subject to the 23

classification procedures for the hazard classes flammable solids or pyrophoric solids. Also other 24

solids that are classified as oxidising solids are normally not flammable, although a few 25

exemptions may exist. Expert judgement should be sought in case of doubt. 26

2.14.4. Classification of substances and mixtures as oxidising solids 27


Oxidising solids may cause, or contribute to, the combustion of other material. Although the 29

definition states that they generally do this by yielding oxygen, halogens can behave in a similar 30

way. Therefore, any substance or mixture containing oxygen and/or halogen atoms should in 31

principle be considered for inclusion into the hazard categories oxidising solids. This does not 32

necessarily mean that every substance or mixture containing oxygen and/or halogen atoms 33

should be subjected to the full testing procedure. 34

2.14.4.1.1. Screening procedures and waiving of testing 35

Solids that are classified as explosives should not be subjected to the testing procedures for 36

oxidising solids. 37

140



Organic peroxides should be considered for classification within the hazard class organic 1

peroxides, see Chapter 2.15 of this guidance. 2

Experience in the handling and use of substances or mixtures which shows them to be oxidising 3

is an important additional factor in considering classification as oxidising solids. In the event of 4

divergence between test results and known experience, judgement based on known experience 5

should take precedence over test results. 6

Before submitting a substance or a mixture to the full test procedure, an evaluation of its 7

chemical structure may be very useful as it may prevent unnecessary testing. The person 8

applying this procedure should have sufficient experience in testing and in theoretical evaluation 9

of hazardous substances and mixtures. The following text provides a guideline for the 10

theoretical evaluation of potential oxidising properties on basis of its composition and chemical 11

structure. In case of doubt, the full test must be performed. 12

For organic substances or mixtures the classification procedure for this hazard class need not to 13

be applied if: 14

a. the substance or mixture does not contain oxygen, fluorine or chlorine; or 15

b. the substance or mixture contains oxygen, fluorine or chlorine and these elements are 16

chemically bonded only to carbon or hydrogen. 17

For inorganic substances or mixtures, the classification procedure for this hazard class need not 18

be applied if they do not contain oxygen or halogen. 19

On basis of this theoretical evaluation only a distinction can be made between ‘potentially 20

oxidising’ (i.e. further testing required) and ‘non-oxidising’ (i.e. no further testing for this 21

hazard class required). It is not possible to assign a hazard category on basis of a theoretical 22

evaluation. 23

Any substance or mixture that complies with the above waiving criteria can be safely regarded 24

to have no oxidising properties and, hence, needs not to be tested and needs not to be 25

regarded as an oxidising solid. However, such a substance or mixture may still possess other 26

hazardous properties that require classification into another hazard class. 27

In case a mixture of an oxidising substance and a non-hazardous inert substance is offered for 28

classification, the following should be taken into account: 29

An inert material by definition does not contribute to the oxidising capability of the 30

oxidising substance. Hence, the mixture can never be classified into a more severe 31

hazard category. 32

If an oxidising substance is mixed with an inert material, the oxidising capability of the 33

mixture does not linearly decrease with decreasing content of oxidising substance. The 34

relationship is more or less logarithmic and depends on the characteristics of the 35

oxidising substance. For instance, a mixture containing 50 % of a strong oxidiser and 50 36

% of an inert material may retain 90 % of the oxidising capability of the original 37

oxidising component. Non-testing classification of mixtures based solely on test data for 38

the original oxidising substance should therefore be done with extreme care and only, if 39

sufficient experience in testing exists. 40


The testing procedures for oxidising solids are based on the capability of an oxidising solid to 42

enhance the combustion of a combustible material. Therefore, solids that are submitted to 43

classification testing are mixed with a combustible material. In principle, dried fibrous cellulose 44

is used as a combustible material. The mixture of the potentially oxidising solid and cellulose is 45

then ignited and its behaviour is observed and compared to the behaviour of reference material 46

mixtures. 47



For solids the mixture with cellulose is ignited at atmospheric conditions and the time necessary 1

for the combustion reaction to consume the mixture is recorded. The faster the combustion 2

rate, the stronger the oxidising capability of the solid tested. 3

Annex I: 2.14.2.1. An oxidising solid shall be classified in one of the three categories for this

class using test O.1 in Part III, sub section 34.4.1 of the UN RTDG, Manual of Tests and

Criteria, in accordance with Table 2.14.1:

Table 2.14.1

Criteria for oxidising solids

Category Criteria using test O.1 Criteria using test O.3

1 Any substance or mixture which, in the

4:1 or 1:1 sample-to-cellulose ratio (by

mass) tested, exhibits a mean burning

time less than the mean burning time of

a 3:2 mixture, (by mass), of potassium

bromate and cellulose.

Any substance or mixture which, in the



rate greater than the mean burning rate

of a 3:1 mixture (by mass) of calcium

peroxide and cellulose.




time equal to or less than the mean

burning time of a 2:3 mixture (by mass)

of potassium bromate and the criteria

for Category 1 are not met.




rate equal to or greater than the mean

burning rate of a 1:1 mixture (by mass)

of calcium peroxide and cellulose and

the criteria for Category 1 are not met.




time equal to or less than the mean

burning time of a 3:7 mixture (by mass)

of potassium bromate and cellulose and

the criteria for Categories 1 and 2 are

not met.




rate equal to or greater than the mean

burning rate of a 1:2 mixture (by mass)

of calcium peroxide and cellulose and

the criteria for Categories 1 and 2 are

not met.

Note 1

Some oxidising solids also present explosion hazards under certain conditions (when stored in

large quantities). Some types of ammonium nitrate may give rise to an explosion hazard

under extreme conditions and the 'Resistance to detonation test' (IMSBC Code (International

Maritime Solid Bulk Cargoes Code, IMO), Appendix 2, Section 5) can be used to assess this

hazard. Appropriate information shall be made in the SDS.

Note 1 may also apply to other oxidising ammonium salts. Experience indicates that the 4

conditions required for ammonium nitrate to present an explosion hazard involve a combination 5

of factors, such as storage in large volumes (multiple tonnes) and either contamination (e.g. 6

with metals, acids, organics) or excessive heat (e.g. under conditions of fire). The resistance to 7

detonation (RTD) test is extensively described in Regulation (EC) No 2003/2003 for ammonium 8

nitrate. 9

For additional information regarding the use of non-testing data see Section 2.14.4.3 below and 10

Urben, 2007 (see Section 2.14.7). 11

142




The test methods18 for oxidising solids are designed to give a final decision regarding their 2

classification. Apart from testing, also experience in the handling and use of substances or 3

mixtures which shows them to be oxidising is an important additional factor in considering 4

classification in these hazard classes. In the event of divergence between test results and 5

known experience, judgement based on known experience should take precedence over test 6

results. However, a substance or mixture must not be classified into a less severe Category 7

based on experience only. 8


Classification of oxidising solids is done according to decision logic 2.14 as included in the GHS. 10

NOTE: The person responsible for the classification of oxidising solids should be


18 As from December 2012 an alternative test method for oxidising solids, Test O.3, has been included in the UN MTC (see document ST/SG/AC.10/40/Add.2). Test O.3 is an improved version of Test O.1 using a

different reference substance and gravimetric measurements of the burning rate. Reference to Test O.3 has been included in the 5th revised edition of the GHS.



Figure 2.14.4—a Decision logic for oxidising solids (Decision logic 2.14 of GHS) 1

2

The substance/mixture is a solid

Does it, in the 4:1 or 1:1 sample-to-cellulose, by mass, tested ignite or burn?

Does it, in the 4:1 or 1:1 sample-to-cellulose, by mass, tested

exhibit a mean burning time ≤ the mean burning time of a 3:7

mixture, by mass, by potassium bromate and cellulose?

Or

a mean burning rate greater than or equal to the mean burning

rate of a 1:2 mixture, by mass, of a calcium peroxide and

cellulose?


exhibit a mean burning time ≤ the mean burning time of a 2:3


Or

a mean burning rate greater than or equal to the mean burning

rate of a 1:1 mixture, by mass, of a calcium peroxide and

cellulose?


exhibit a mean burning time < the mean burning time of a 3:2


Or

a mean burning rate greater than the mean burning rate of a 3:1

mixture, by mass, of a calcium peroxide and cellulose?

Category 1

Danger

Category 2

Warning

Category 3

Warning

Not classified

Not classified

Yes

Yes

Yes

Yes

No

No

No

No

144



2.14.4.5. Hazard communication for oxidising solids 1

2.14.4.5.1. Pictograms, signal words, hazard statements and precautionary 2

statements 3

The symbols and hazard statements are designed to indicate that oxidising substances and 4

mixtures may cause or contribute to fire or explosion and therefore in principle should be 5

separated from combustible materials. 6


Label elements for oxidising solids

Category 1 Category 2 Category 3

Symbol


Hazard Statement H271: May cause fire or

explosion; strong oxidiser

H272: May intensify

fire; oxidiser

H272: May intensify

fire; oxidiser

Precautionary

Statement Prevention

P210

P220

P280

P283

P210

P220

P280

P210

P220

P280

Precautionary

Statement Response

P306 + P360

P371 + P380 + P375

P370 + P378

P370 + P378 P370 + P378

Precautionary

Statement Storage P420

Precautionary

Statement Disposal P501 P501 P501



Division 5.1 within Class 5 of the UN RTDG Model Regulations covers oxidising liquids and 9

oxidising solids, using the same tests and criteria as the CLP. Therefore, a solid substance or 10

mixture classified as Division 5.1 (sometimes referred to as Class 5.1) according to any of the 11

modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO TI) is normally also 12

classified as an oxidising solid according to the CLP. Packing Groups I, II and III of the transport 13

regulations correspond directly to Categories 1, 2 and 3 of the CLP, respectively. See Annex VII 14

for additional information on transport classification in relation to CLP classification. 15



2.14.6. Examples of classification for oxidising solids 1


criteria 3

The list of substances and mixtures fulfilling the criteria for classification is only presented for 4

information purposes. This list is not exhaustive. For examples of results see section 34.4.1.5 of 5

UN-MTC. 6

Calcium nitrate, anhydrous 7

Chromium trioxide 8

Potassium nitrite 9

Potassium perchlorate 10

Potassium permanganate 11

Sodium chlorate 12

Sodium nitrite 13

Sodium nitrate 14

Strontium nitrate, anhydrous 15



Calcium nitrate, tetrahydrate 18

Cobalt nitrate, hexahydrate 19

2.14.7. Reference 20



146



2.15. ORGANIC PEROXIDES 1


The criteria for ‘Organic peroxides’ are found in Annex I, Section 2.15 of CLP and are identical to 3


The hazard class organic peroxides is unique in the respect that it is the only category to which 5

chemicals are assigned on the basis of their chemical structure. Organic peroxides cannot be 6

seen as an ‘intrinsic property’; it is a family of chemical substances and mixtures which may 7

have various properties. However, the type of peroxide is determined by testing. 8

2.15.2. Definitions and general considerations for the classification of organic 9

peroxides 10

In CLP, the following definition is given for organic peroxides. 11


In addition to the definition (CLP Annex I, 2.15.1), organic peroxides may: 13

a. be flammable; 14

b. emit flammable gas when heated. 15

In general, organic peroxides do not have or have only weak oxidising properties. 16

The additional (subsidiary) labelling, as indicated in the list of classified organic peroxides 17

included in the UN RTDG Model Regulations, Section 2.5.3.2.4, represents the additional 18

hazardous properties. 19



Organic peroxides means liquid or solid organic substances which contain the bivalent -O-O-

structure and may be considered derivatives of hydrogen peroxide, where one or both of the

hydrogen atoms have been replaced by organic radicals. The term organic peroxide includes

organic peroxide mixtures (formulations) containing at least one organic peroxide. Organic

peroxides are thermally unstable substances or mixtures, which can undergo exothermic self-

accelerating decomposition. In addition, they can have one or more of the following

properties:

(i) be liable to explosive decomposition;

(ii) burn rapidly;

(iii) be sensitive to impact or friction;

(iv) react dangerously with other substances.

2.15.1.2. An organic peroxide is regarded as possessing explosive properties when in

laboratory testing the mixture (formulation) is liable to detonate, to deflagrate rapidly or to

show a violent effect when heated under confinement.



Neither the burning properties nor the sensitivity to impact and friction form part of the 1

classification procedure for organic peroxides in CLP. However, these properties may be of 2

importance for the safe handling of organic peroxides (see Section 2.15.4.3.2, additional 3

testing). 4

In addition, the following should be noted: 5


The explosive properties do not have to be determined according to the CLP Annex I, Chapter 7

2.1, because explosive properties are incorporated in the decision logic for organic peroxides. 8

Note that organic peroxides may have explosive properties when handled under higher 9

confinement. 10

Flammable properties 11

The hazard statement for flammable properties for liquid organic peroxides should be based on 12

the appropriate category for flammable liquids, as long as the flash point is relevant, (see 13

Section 2.15.4.3.2). The translation table in Annex VII to CLP can be used for this. 14

2.15.4. Classification of substances and mixtures as organic peroxides 15


The classification of an organic peroxide in one of the seven categories ‘Types A to G’ is 17

dependent on its detonation, deflagration and thermal explosion properties, its response to 18

heating under confinement, its explosive power and the concentration and the type of diluent 19

added to desensitize the organic peroxide. Specifications of acceptable diluents that can be used 20

safely are given in the UN RTDG Model Regulations, 2.5.3.5. The classification of an organic 21

peroxide as Type A, B or C is dependent on the type of packaging in which the organic peroxide 22

is tested as it affects the degree of confinement to which the organic peroxide is subjected. This 23

has to be considered when handling the organic peroxide; stronger packaging may result in 24

more violent reactions when the organic peroxide decomposes. This is why it is important that 25

storage and transport is done in packaging, allowed for the type of organic peroxide, that 26

conforms the requirements of the UN-packaging or IBC instruction (P520/IBC520) or tank 27

instruction (T23). 28

The traditional aspects of explosive properties, such as detonation, deflagration and thermal 29

explosion, are incorporated in the decision logic of CLP Figure 2.15.1. Consequently, explosive 30

property determination as prescribed for the hazard class ‘explosives’ needs not to be 31

conducted for organic peroxides. 32

A list of currently classified organic peroxides is included in the UN RTDG Model regulations, 33

Section 2.5.3.2.4. 34


In CLP, organic peroxides are not classified as oxidisers but they are a distinct hazard class. 36

Annex I: 2.15.2.1. Any organic peroxide shall be considered for classification in this class,

unless it contains:

a) not more than 1,0 % available oxygen from the organic peroxides when containing not

more than 1,0 % hydrogen peroxide; or

b) not more than 0,5% available oxygen from the organic peroxides when containing more

than 1,0 % but not more than 7,0 % hydrogen peroxide.

[…]

148



In CLP decision logic Annex I, Figure 2.15.1, classification of organic peroxides is based on 1

performance based testing both small scale tests and, where necessary, some larger scale test 2

with the organic peroxide in its packaging. The concept of ‘intrinsic properties’ is, therefore, not 3

applicable to this hazard class. 4

Organic peroxides are classified into one of the seven categories of ‘Types A to G’ according to 5

the classification criteria of CLP. The classification principles are given in decision logic Figure 6

2.15.1 of CLP and the Test Series A to H, as described in the Part II of the UN-MTC, should be 7

performed. 8

Annex I: 2.15.2.2. Organic peroxides shall be classified in one of the seven categories of

‘Types A to G’ for this class, according to the following principles:

(a) any organic peroxide which, as packaged, can detonate or deflagrate rapidly shall be

defined as organic peroxide TYPE A;

(b) any organic peroxide possessing explosive properties and which, as packaged, neither

detonates nor deflagrates rapidly, but is liable to undergo a thermal explosion in that

package shall be defined as organic peroxide TYPE B;

(c) any organic peroxide possessing explosive properties when the substance or mixture as

packaged cannot detonate or deflagrate rapidly or undergo a thermal explosion shall be

defined as organic peroxide TYPE C;

(d) any organic peroxide which in laboratory testing:

(i) detonates partially, does not deflagrate rapidly and shows no violent effect when


(ii) does not detonate at all, deflagrates slowly and shows no violent effect when


(iii) does not detonate or deflagrate at all and shows a medium effect when heated

under confinement;

shall be defined as organic peroxide TYPE D;

(e) any organic peroxide which, in laboratory testing, neither detonates nor deflagrates at all

and shows low or no effect when heated under confinement shall be defined as organic

peroxide TYPE E;

(f) any organic peroxide which, in laboratory testing, neither detonates in the cavitated state

nor deflagrates at all and shows only a low or no effect when heated under confinement as

well as low or no explosive power shall be defined as organic peroxide TYPE F;

(g) any organic peroxide which, in laboratory testing, neither detonates in the cavitated state

nor deflagrates at all and shows no effect when heated under confinement nor any

explosive power, provided that it is thermally stable, i.e. the SADT is 60 oC or higher for a

50 kg package(1), and, for liquid mixtures, a diluent having a boiling point of not less than

150 oC is used for desensitisation, shall be defined as organic peroxide TYPE G. If the

organic peroxide is not thermally stable or a diluent having a boiling point less than 150 oC

is used for desensitisation, the organic peroxide shall be defined as organic peroxide

TYPE F.

Where the test is conducted in the package form and the packaging is changed, a further test

shall be conducted where it is considered that the change in packaging will affect the outcome

of the test.

(1) See UN RTDG, Manual of Test and Criteria, sub-sections 28.1, 28.2, 28.3 and Table 28.3.



A list of currently classified organic peroxides is included in the UN RTDG Model Regulations, 1

Section 2.5.3.2.4. 2


2.15.4.3.1. Thermal stability tests and temperature control 4

In addition to the classification tests given in decision logic Figure 2.15.1 of CLP, the thermal 5

stability of the organic peroxide has to be assessed in order to determine the SADT. For the 6

determination of the SADT, the testing method in UN-MTC, Part II, Section 28, may be used. 7

The SADT is defined as the lowest temperature at which self-accelerating decomposition of an 8

organic peroxide may occur in the packaging as used in transport, handling and storage. The 9

SADT is a measure of the combined effect of the ambient temperature, decomposition kinetics, 10

package size and the heat transfer properties of the organic peroxide and its packaging. 11

There is no relation between the SADT of an organic peroxide and its classification in one of the 12

seven categories ‘Types A to G’. The SADT is used to derive safe handling, storage and 13

transport temperatures (control temperature) and alarm temperature (emergency 14

temperature). 15

Depending on its SADT an organic peroxide needs temperature control and the rules as given in 16

CLP Annex I, 2.15.2.3, consist of the following two elements: 17

1. Criteria for temperature control: 18

The following organic peroxides need to be subjected to temperature control: 19

a. Organic peroxide types B and C with a SADT ≤ 50 ° C; 20

b. Organic peroxide type D showing a medium effect when heated under confinement 21

with a SADT ≤ 50 ° C or showing a low or no effect when heated under 22

confinement with a SADT ≤ 45 ° C; and 23

c. Organic peroxide types E and F with a SADT ≤ 45 ° C. 24

2. Derivation of control and emergency temperatures: 25

Type of receptacle SADT * Control temperature Emergency temperature

Single packagings and IBC’s

20 °C or less

over 20 °C to 35 °C

over 35 °C

20 °C below SADT

15 °C below SADT

10 °C below SADT

10 °C below SADT

10 °C below SADT

5 °C below SADT

Tanks < 50 °C 10 °C below SADT 5 °C below SADT

* i.e. the SADT of the organic peroxide as packaged for transport, handling and storage 26

It should be emphasized that the SADT is dependent on the nature of the organic peroxide 27

itself, together with the volume and heat-loss characteristics of the packaging or vessel in which 28

the organic peroxide is handled. The temperature at which self-accelerating decomposition 29

occurs falls: 30

as the size of the packaging or vessel increases; and 31

with increasing efficiency of the insulation on the package or vessel. 32

The SADT is only valid for the organic peroxide as tested and when handled properly. Mixing the 33

organic peroxide with other chemicals, or contact with incompatible materials (including 34

incompatible packaging or vessel material) may reduce the thermal stability due to catalytic 35

150



decomposition, and lower the SADT. This may increase the risk of decomposition and has to be 1

avoided. 2

2.15.4.3.2. Additional considerations and testing 3


The sensitivity of organic peroxides to impact (solids and liquids) and friction (solids only) may 5

be of importance for the safe handling of the organic peroxide if they have pronounced 6

explosive properties (e.g. they are liable to detonate, to deflagrate rapidly or show a violent 7

effect when heated under confinement). Test methods to determine these properties are 8

described in Test Series 3 of the UN-MTC (see Test 3 (a) (ii) and 3 (b) (i)). This information on 9

the mechanical sensitivity should be included in the SDS. 10


In some national storage guidelines the burning rate is commonly used for classification for the 12

purposes of storage and consequential storage requirements. Test methods are incorporated in 13

these national storage regulations. 14

Flash point 15

The flash point for liquid organic peroxides is only relevant in the temperature range where the 16

organic peroxide is thermally stable. Above the SADT of the organic peroxide determination of 17

the flash point is not relevant because decomposition products are evolved. 18

NOTE: In case a flash point determination seems reasonable (expected flash point below

the SADT) a test method using small amount of sample is recommended. In case the

organic peroxide is diluted or dissolved, the diluent may determine the flash point.

Auto-ignition temperature 19

The determination of the auto ignition temperature is not relevant for organic peroxides. 20

Available test methods are for non-decomposing vapour phases but the vapours of organic 21

peroxides decompose during execution of the test and auto ignition of these organic peroxide 22

vapours can never be excluded. This information should be included in the SDS. 23

Self-ignition temperature 24

Also the determination of the self-ignition temperature (applicable for solids) is not relevant. 25

The thermal stability of organic peroxides is quantitatively given by the SADT. 26

Control and Emergency temperatures 27

The Control and Emergency temperatures are based on the SADT as in most cases determined 28

by UN Test H.4. The Dewar vessel used in the UN Test H.4 is supposed to be representative for 29

the organic peroxide handled in packages. For handling the organic peroxide in larger quantities 30

(IBCs/tanks/vessels etc.) and/or in (thermally) insulated containers, the SADT has to be 31

determined for that quantity with that degree of insulation. From that SADT the Control and 32

Emergency temperatures can be derived (see also Section 2.15.4.3.1). 33

2.15.4.3.3. Additional classification considerations 34

Currently the following properties are not incorporated in the classification of organic peroxides 35

under the CLP: 36

mechanical sensitivity i.e. impact and friction sensitivity (for handling purposes); 37

burning properties (for storage purposes); 38

flash point for liquids; and 39

burning rate for solids. 40



Furthermore: 1

Annex I: 2.15.4.2. Mixtures of already classified organic peroxides may be classified as the

same type of organic peroxide as that of the most dangerous component. However, as two

stable components can form a thermally less stable mixture, the SADT of the mixture shall

be determined.

Note: The sum of the individual parts can be more hazardous than the individual

components.

Formulated commercial organic peroxides are classified according to their SADT. 2


The decision logic for organic peroxides is applicable according to CLP. 4

NOTE: The person responsible for the classification of organic peroxides should be


5

152



Figure 2.15.4—a Decision logic 2.15 for organic peroxides 1

2



2.15.5. Hazard communication for organic peroxides 1


statements 3

According to CLP the following label elements must be used for organic peroxide meeting the 4

criteria for this hazard class: 5


Label elements for organic peroxides

Classification Type A Type B Type C & D Type E & F Type G

GHS

pictograms

There are no

label elements

allocated to

this hazard

category

Signal Word Danger Danger Danger Warning

Hazard

Statement

H240:

Heating may

cause an

explosion

H241:

Heating may

cause a fire

or explosion

H242:

Heating may

cause a fire

H242:

Heating may

cause a fire

Precautionary

statement

Prevention

P210

P234

P235

P240

P280

P210

P234

P235

P240

P280

P210

P234

P235

P240

P280

P210

P234

P235

P240

P280

Precautionary

statement

Response

P370+P372+

P380+P373

P370+P380+

P375[+P378]1

P370+P378 P370+P378

Precautionary

statement

Storage

P403

P410

P411

P420

P403

P410

P411

P420

P403

P410

P411

P420

P403

P410

P411

P420

Precautionary

statement

Disposal

P501 P501 P501 P501

154



1 See introduction to Annex I for details on the use of square brackets.


2.15.5.2. Additional labelling provisions for organic peroxides 2

Additional hazardous properties, resulting in additional (subsidiary) labelling, are indicated in 3

the list of classified organic peroxides included in the UN RTDG Model Regulations, section 4

2.5.3.2.4. 5


Division 5.2 within Class 5 of the UN RTDG Model Regulations covers organic peroxides. A list of 7

currently classified organic peroxides is included in the UN RTDG Model Regulations, Section 8

2.5.3.2.4. This table includes organic peroxides Type B - Type F (and some formulations Type 9

G, so-called exempted organic peroxides). 10

An exceptional case in this respect is a peroxyacetic acid formulation, as currently classified in 11

the UN RTDG Model Regulations under UN 3149, with the following description: HYDROGEN 12

PEROXIDE AND PEROXYACETIC ACID MIXTURE with acid(s), water and not more than 5 % 13

peroxyacetic acid, STABILISED. In the classification procedure for organic peroxides, see 14

decision logic in Section 2.15.4.4, this formulation will be assigned to organic peroxide Type G, 15

and consequently no label elements are allocated. In view of the above, this formulation can be 16

classified, also in accordance with CLP, as an Oxidising liquid, Category 2. See Annex VII for 17


2.15.7. Examples of classification for organic peroxides 19


criteria 21

Substance to be classified: Example Peroxide 22

Molecular formula: n.a. 23

According to CLP Annex I, Section 2.15.2.1, the substance has an active oxygen content of 7.40 24

% and thus has to be considered for classification in the hazard class organic peroxides. 25

Test results and classification according to CLP decision logic 2.15.1 for organic peroxides and 26

the UN-MTC, Part II, is as follows: 27


1. Name of the organic peroxide: Example Peroxide

2. General data

2.1. Composition: Example Peroxide, technically pure (97 %)

2.2. Molecular formula: n.a.

2.3. Active oxygen content: 7.18 %

2.4. Physical form: liquid

2.5. Colour: colourless

2.6. Density (apparent): 900 kg/m3




3. Detonation (test series A)

Box 1 of the decision logic: Does the peroxide propagate a detonation?

3.1. Method: UN Test A.1: BAM 50/60 steel tube test

3.2. Sample conditions: peroxide assay 97 %

3.3. Observations: fragmented part of the tube: 18 cm

3.4. Result: No

3.6. Exit: 1.3

4. Deflagration (test series C)

Box 5 of the decision logic: Can the peroxide propagate a deflagration?

4.1. Method 1: Time/pressure test (test C.1)

4.1.1. Sample conditions: ambient temperature

4.1.2. Observations: 4000 ms

4.1.3. Result: Yes, slowly

4.2. Method 2: Deflagration test (test C.2)

4.2.1. Sample conditions: temperature: 25 °C

4.2.2. Observations: deflagration rate: 0.74 mm/s

4.2.3. Result: Yes, slowly

4.3. Final result: Yes, slowly

4.4. Exit: 5.2

5. Heating under confinement (test series E)

Box 8 of the decision logic: What is the effect of heating it under confinement?

5.1. Method 1: Koenen test (test E.1)

5.1.1. Sample conditions: -

5.1.2. Observations: limiting diameter: 2.0 mm

fragmentation type ‘F’

5.1.3. Result: Violent

5.2. Method 2: Dutch pressure vessel test

(test E.2)

5.2.1. Sample conditions: -

5.2.2. Observations: limiting diameter: 6.0 mm (with 10 g)

156




5.2.3. Result: Medium

5.3. Final result: Violent

5.4. Exit: 8.1

6. Explosion test in package (test series G)

Box 10 of the decision logic: Can it explode as packaged?

6.1. Method: Thermal explosion test in package (test G.1)

6.2. Sample conditions: 30 litre packaging,

6.3. Observations: no fragmentation (N.F.)

6.4. Result: No

6.5. Exit: 10.2

7. Thermal stability (outside of the decision logic)

7.1. Method: Heat accumulation storage test (test H.4)

7.2. Sample conditions: mass 380 g. Half life time of cooling of Dewar vessel with400 ml DMP:

10.0 hrs. (representing substance in package)

7.3. Observations: self accelerating decomposition at 35 °C

no self accelerating decomposition at 30 °C

7.4. Result: SADT 35 °C

8. General remarks: The decision logic is given in Figure x20

9. Final classification

Hazard class: Organic peroxide, Type C, liquid, temperature controlled

Label: Flame (GHS02)

Signal word: Danger

Hazard statement: H242: Heating may cause a fire

Temperature control: Needed based on SADT (35 °C, in package)

Control temperature*: 20 °C (in package)

Emergency temperature*: 25 °C (in package)

*see UN-MTC, table 28.2. 1

2

20 Not attached to this example.



2.15.7.2. Additional remarks 1


As shown in Section 2.15.7.1 a substance and a mixture may have explosive properties when 3

handled under greater confinement and where the packaging in which it was tested in UN Test 4

G.1 (see point 6 of classification test results above) is changed. Such information should be 5

given in the SDS. 6

The example in Section 2.15.7.1 shows a violent effect when heated under confinement (see 7

point 5.3 of the above results). Consequently, also the impact sensitivity according to UN Test 8

series 3, test 3 (a) (ii), BAM Fallhammer should be determined. For this example it amounts to 9

20 J. Such information should be given in the SDS. 10


For the example in Section 2.15.7.1 the burning properties as determined by the test method 12

described in the storage guidelines, currently in place in France, Germany, Netherlands and 13

Sweden, is 7.0 kg/min/m². Based on this figure and the classification as organic peroxide type 14

C, the storage classification can be assigned in those countries. 15

Flash point 16

The example substance thermally decomposes before the temperature at which the vapour can 17

be ignited is reached (see Section 2.15.4.3.2) and consequently a flash point cannot be 18

determined. 19

158



2.16. CORROSIVE TO METALS 1


The criteria for ‘Corrosive to metals’ are found in Annex I, Section 2.16 of CLP and are identical 3

to those in Chapter 2.16 of GHS21. 4

The hazard class corrosive to metals is a physico-chemical property that is new in the EU 5

classification scheme and appears for the first time in CLP. So far, only the health hazard 6

corrosivity to skin was considered in the classification scheme. To some extent, both properties 7

relate to each other and, in the context of transport of dangerous goods, have been considered 8

for classification in class 8, despite the different nature of the hazard (material damage versus 9

living tissue damage). 10

A substance or a mixture that is corrosive to metal under normal conditions is a substance or a 11

mixture liable to undergo an irreversible electrochemical reaction with metals that leads to 12

significant damage or, in some cases, even to full destruction of the metallic components. The 13

corrosive to metal property is a quite complex property, since it is a substance (or mixture) 14

related as well as a material (metal) related property. This means a corrosive substance or 15

mixture leads to corroded material (metal), according to a number of external conditions. From 16

the material side, many types of corrosion processes may occur, according to configurations, 17

liquid or fluid media inducing the corrosion process, nature of metal, potential passivation 18

occurring by oxide formation during corrosion. 19

From the substance or mixture side, many parameters may influence the corrosion properties of 20

a substance or mixture, such as the nature of the chemical or the pH. From an electochemistry 21

point of view, corrosion conditions are often studied using Pourbaix diagrams, which plot the 22

electrochemical potential (in Volt) that develops according to electrical charges transfer versus 23

the pH-value. Such a diagram is shown for the case of iron and applies only for carbon steel 24

corrosion (Jones, 1996). 25




Figure 2.16.1—a Potential pH (also called Pourbaix) diagram for iron in water at 25 °C, 1 indicating stable form of the Fe element and implicitly, corrosion domains 2

3

For the purposes of CLP, corrosion to metal will only be considered, by pure convention, for 4

substances and mixtures that are liable to attack carbon steel or aluminium, two of the most 5

common metals that may come in contact with chemical substances (containment material, 6

reactor material). The classification scheme applied here must not be considered as a material 7

(metal) classification method for metals regarding resistance to corrosion. By no means steel or 8

aluminium specimens that are treated to resist to corrosion, must be selected for testing. 9


substances and mixtures corrosive to metals 11

CLP comprises the following definition for substances and mixtures that are corrosive to metal. 12


A substance or a mixture that is corrosive to metals means a substance or a mixture which by

chemical action will materially damage, or even destroy, metals.


There is no direct relation to other physical hazards. 14

2.16.4. Classification of substances and mixtures as corrosive to metals 15


Importance of the physical state of the test substance or mixture 17

There is no reference in the definition (CLP Annex I, 2.16.1) to the physical state of the 18

substances or mixtures that needs consideration for potential classification in this hazard class. 19

According to the test method to be employed for considering classification under this hazard 20

class, we may state at least that gases are out of the scope of the corrosive to metal hazard 21

class. Neither the corrosivity of gases nor the formation of corrosive gases is currently covered 22

by CLP classes and are therefore not applicable here. 23

160



According to the classification criteria only substances and mixtures for which the application of 1

the UN Test C.1 (described in part III, Section 37.4.1.1 of the UN-MTC) is relevant and needs to 2

be considered. Application of classification criteria in the UN-MTC, Section 37.4 excludes solids, 3

while ‘liquids and solids that may become liquids (during transport)’, have to be considered for 4

such a classification. 5

The wording ‘solids that may become liquids’ was developed for UN RTDG Model Regulations 6

classification purposes, and needs further explanation. Solids may become liquids by melting 7

(due to increase in temperature). Solids having a melting point lower than 55 °C (which is the 8

test temperature required in UN Test C.1) must then be taken into consideration. The other 9

physical way to transform a solid into liquid is by dissolution in water or another solvent. 10

Classification of solid substances that may become liquids by dissolution is subject to further 11

expert judgement, and may need adaptation of the classification criteria or test protocol (see 12

Section 2.16.4.4.2). Interaction with liquids may come from air moisture or unintentional 13

contact with water. Other solvent traces may result from the extraction process during 14

manufacturing and these may induce corrosion in practice. 15

Substances and mixtures in a liquid state must be tested without any modification before 16

testing. For other cases (solids that may become liquids), appropriate testing procedures 17

require further work by the Committees of experts in charge of developing and updating the 18

GHS at UN level. It needs to be further specified how such substances or mixtures must be 19

prepared (transformed into liquids) to be able to determine their corrosivity to metals. As an 20

example, it is thought that the quantity of solvent (water or any other solvent) to liquefy the 21

test substance before testing would greatly influence results of the UN Test C.1 test and may 22

not necessarily represent the real life situation of a product during transport, handling or use. 23

Non-testing data 24

Following parameters are helpful to evaluate corrosive properties before testing: 25

melting points for solids; 26

chemical nature of the substances and mixtures under evaluation (e.g. strong acids); 27

pH values (liquids). 28

See also IR & CSA, Chapter R.7a: Endpoint specific guidance, Section R.7.1.2 (Melting 29

point/freezing point). 30

Literature may also provide information on widely used substances and liquids ‘compatibility 31

tables’, taking account of the corrosiveness of the products that may serve to decide whether 32

testing must be conducted before assigning the corrosive to metals hazard class, on basis of 33

expert judgement. 34

The following substances and mixtures should be considered for classification in this class: 35

substances and mixtures having acidic or basic functional groups; 36

substances or mixtures containing halogen; 37

substances able to form complexes with metals and mixtures containing such 38

substances. 39


Experience may have proven the corrosivity of given substances and mixtures. In such case no 41

more testing is needed (see examples in Section 2.16.7). 42

Generally extreme pH-values point to a higher likelihood that the substance or mixture is 43

corrosive. However, it cannot lead to immediate classification in the hazard class corrosive to 44



metals. As a proof of that, Figure 2.16.1—a shows that immunity zones (where steel does not 1

corrode) still exist on the full spectrum of pH values as far as carbon steel is concerned. 2

Corrosivity is so complex that the evaluation of a mixture cannot be extrapolated from similar 3

behaviour of constituents of a mixture. However, if one significant component of a mixture is 4

corrosive to metals the mixture is likely to be corrosive to metals as well. Testing the actual 5

mixture is therefore highly recommended. As already mentioned, solids are currently difficult to 6

test according to the current CLP requirements, as the UN Test C.1 was designed for liquids. 7

Where an initial test on either steel or aluminium indicates the substance or mixture being 8

tested is corrosive, the follow up test on the other metal is not required. 9


Substances and mixtures of hazard class corrosive to metals are classified in a single hazard 11

category on the basis of the outcome of the UN Test C.1 (UN-MTC, Part III, Section 37, 12

paragraph 37.4). 13


Criteria for substances and mixtures corrosive to metals

Category Criteria

1 Corrosion rate on either steel or aluminium surfaces exceeding 6,25 mm per

year at a test temperature of 55 oC when tested on both materials.


2.16.4.4.1. General considerations 15

It is important to point out that the criteria of corrosion rate will never be applied in an absolute 16

way, but by extrapolating the measured rate of corrosion over the test period to the annual 17

assumed correlating corrosion rate. This exercise has to take account of the fact that the 18

corrosion rate is not necessarily constant over time. Expert judgement may be required to 19

consolidate the optimum test duration and to ascertain test results. However, the possibility of 20

increasing the testing period from minimum one week to four weeks as well as the use of two 21

different metals in the UN Test C.1 act as barriers against erroneous classification. 22

Whatever the result of the classification may be, the classification as corrosive to metals relates 23

to steel and/or aluminium only and does not provide information with regard to the corrosivity 24

potential to other metals than those tested. 25

Two types of corrosion phenomena need to be distinguished for classification of substances and 26

mixtures in this hazard class, although not reported in CLP: the uniform corrosion attack and 27

the localised corrosion (e.g. pitting corrosion, shallow pit corrosion). 28

Table 2.16.4—a (Section 37.4.1.4.1 of the UN- MTC) translates the corresponding minimum 29

mass loss rates leading to classify the test substance or mixture as corrosive to metals for 30

standard metal specimens (2 mm of thickness), according to time of exposure, for reasons of 31

uniform corrosion process. In case of use of metal plates of a thickness that differs from the 32

specified 2 mm (see comments in Section 2.4.2), the values in tables Table 2.16.4—a and Table 33

2.16.4—b need adjustments due to the fact that the corrosion process depends on the surface 34

of specimen. 35

162



Table 2.16.4—a Minimum mass loss of specimens after different exposure times 1 (corresponding to the criterion of 6.25 mm/year) 2

Exposure time Mass loss

7 days 13.5 %

14 days 26.5 %

21 days 39.2 %

28 days 51.5 %

Table 2.16.4—b (Section 37.4.1.4.2 of the UN-MTC) indicates the criteria leading to 3

classification of the test substance or mixture as corrosive to metals for standard metal 4

specimens, according to time of exposure, for reasons of localised corrosion process. 5

Table 2.16.4—b Minimum intrusion depths after exposure times (corresponding to the 6 criterion of localized corrosion of 6.25 mm/year) 7

Exposure time Min. intrusion depth

7 days 120 m

14 days 240 m

21 days 360 m

28 days 480 m

It is not mentioned explicitly in the text that localised corrosion as well as uniform corrosion has 8

also be taken into account. However, localised corrosion, that is entirely part of UN Test C.1 9

protocol, has actually to be taken into account. In addition, although the type of corrosion is not 10

reflected in the classification result, this valuable information should be given in the SDS 11

. 12



2.16.4.4.2. Additional notes on best practice for testing 1

Competence required for testing 2

The overall evaluation of appropriate data for considering the corrosion properties of a 3

substance or a mixture and in particular for testing it according to the mentioned criteria for this 4

hazard class requires certain qualifications and experience. Expertise is often needed for this 5

hazard class, which relates to a complex and multi-faceted hazardous phenomenon. 6

Selection of metal specimens 7

CLP refers to two types of metals (carbon steel and aluminium) meeting accurate specifications 8

(technical characteristics of metal sheets and plate thickness). Thicker metal sheets, such as 9

cast materials, of which the thickness is reduced by any form of mechanical treatment, may 10

never be used. Mechanical reduction of sheet (metal) thickness could induce corrosion enhanced 11

process due to cross section heterogeneity in metal grain and impurities. It is far better to use 12

slightly different specifications of metal in the correct thickness or slightly different specimen 13

plate thicknesses. It is recognised that it will not always be easy to obtain metal specimens with 14

the profile as described above. 15

Regarding the type of aluminium or steel to be used for this test see UN-MTC, Sub-section 16

37.4.1.2. 17

Minimum corrosive media volume 18

In order to prevent any limitation on the corrosion process due to full consumption of the 19

corrosive media before the end of the testing period, a minimum volume of substance or 20

mixture (1.5 L, according to the UN-MTC) has to be used. (Note: volume/surface ratio of 10 21

mL/cm² is stated in DIN 50905, similar in ASTM G31–72.) 22

Adjustment of the test temperature 23

Corrosion processes are temperature dependent. In the context of CLP, the property corrosive 24

to metals is assessed through testing metal specimens at a specified temperature of 55 °C 1 25

°C. In practice, it may be difficult with standard testing equipment to stay within the 26

temperature window (55 °C 1 °C) of the gas phase, all over the test period. In such case, the 27

test can be performed conservatively at a slightly higher temperature and somewhat lower 28

accuracy (e.g. 57 °C 3 °C). 29

Selecting the appropriate test duration 30

The evaluation of the criterion of 6.25 mm/year is generally based on a test duration not 31

exceeding 1 month. There is, however, the option to stop the test procedure already after 1 32

week (see table 1). For the decision on test duration, the non-linear behaviour of the corrosion 33

process must be taken due account of. In borderline cases a non-appropriate test duration may 34

result in either false positive or false negative results. 35

Specimen cleaning 36

Attention must be paid to the correct cleaning of the corroded residue before measurement of 37

the corrosion characteristics. In case of adhesive corroded layer, the same cleaning process 38

needs to be carried out on a non corroded sample to verify if the cleaning procedure is not 39

significantly abrasive. For further information see UN-MTC, Sub-section 37.4.1.3. 40

Testing soluble solids 41

As said in Section 2.15.4.1, for solids that may become liquids through dissolution in water or in 42

a solvent, the adequate testing procedure is more complex (not explicitly describe in the UN C.1 43

test protocol). In no case will simple dilution of the solid substance or mixture in any quantity of 44

water lead to satisfactory testing of the substance or mixture for corrosion to metals. 45

164



For the specific case where the corrosion potential is linked to the presence of solvent traces 1

(other than water), expert judgement is needed to determine if further testing must be 2

performed (where the solid is put in interaction with the metallic part considered). 3

Example of equipment relevant for the performance UN Test C.1 4

5

Figure 2.16.4—a Example of testing equipment available on the market to perform UN Test C.1 6

7

8




Classification of substances and mixtures corrosive to metals is done according to decision 2

logics 2.16.4.1 as included in the GHS. 3

NOTE: The person responsible for the classification of substances and mixtures corrosive to

metals should be experienced in this field and be familiar with the criteria for classification.

Figure 2.16.4—b Decision logic for substances and mixtures corrosive to metals (Decision logic 4 2.16 of GHS) 5

6

7

8

Substance/mixture

Does it corrode on either steel or aluminium surfaces at a

rate exceeding 6.25 mm/year at a test temperature of 55 °C

when tested on both materials?

Category 1

Warning

Not classified

Yes

No

166



2.16.5. Hazard communication for substances and mixtures corrosive to 1

metals 2


statements 4

Table 2.16.2 of CLP Annex I provides the label elements for hazard class corrosive to metals. 5

The hazard statement H290, using the wording ‘may’, reflects that classification under this 6

hazard class does not cover all metals (testing only considers carbon steel and aluminium). 7

Thus we may find examples of substances and mixtures that are classified in this hazard class 8

corrosive to metals but will not induce corrosive action on other more corrosive resistant metals 9

(e.g. platinum) than those serving as reference materials. 10

Label elements must be used for substances and mixtures meeting the criteria for classification 11

in this hazard class in accordance with Table 2.16.2. 12

Annex I: 2.16.3. Table 2.16.2

Label elements for substances and mixtures corrosive to metals


GHS Pictogram

Signal Word Warning

Hazard Statement H290: May be corrosive to metals

Precautionary Statement, Prevention P234

Precautionary Statement, Response P390

Precautionary Statement, Storage P406

Precautionary Statement, Disposal

Note:

Where a substance or mixture is classified as corrosive to metals but not corrosive to skin and/or eyes, the labelling provisions set out in section 1.3.6 shall be used.


Further, in section 1.3.6 of CLP Annex I a derogation from labelling requirements for substances 14

or mixtures classified as corrosive to metals but not corrosive to skin and/or eyes is provided. 15

Annex I: 1.3.6 Substances or mixtures classified as corrosive to metals but not

classified as skin corrosion or as serious eye damage (Catgory 1)

Substances or mixtures classified as corrosive to metals but not classified as skin corrosion

or as serious eye damage (Catgory 1) which are in the finished state as packaged for consumer use do not require on the label the hazard pictogram GHS05.




Class 8 of the UN RTDG Model Regulations covers substances and mixtures that are classified 2

for corrosivity to skin, metals or both. Valuable information can be obtained from UN RTDG 3

Model Regulations and the modal transport regulations (ADR, RID, ADN and IMDG Code, ICAO 4

TI). Existing test results obtained in the context of the modal transport regulations (ADR, RID, 5

ADN and IMDG Code, ICAO TI) may be applied since the UN Test C.1 serves as reference for 6

testing in both classification systems. See Annex VII for additional information on transport 7


2.16.7. Examples of classification for substances and mixtures corrosive to 9

metals 10

The following table lists some examples of substances and mixtures that should be classified or 11

not in Class 2.16 (according to known UN Test C.1 results) in comparison with predicted results 12

for skin corrosion hazard. 13

Table 2.16.7—a Examples of classified and non classified substances and mixtures in Class 14 2.16 15

Note: ‘Corroded’ means corrosion attack in the sense of UN Test C.1; 16

‘Not corroded’ means corrosion resistant in the sense of UN Test C.1; 17

‘Positive’ or ‘Negative’ are results from skin corrosion. 18

Substance or mixture Steel Aluminium

CLP Annex I, 2.16 classification

Skin (for comparison)

Hydrofluoric acid

> 70 % (UN1790)

Not corroded Corroded Classified Positive

Highly concentrated nitric acid (97 %) (UN2031)

Not corroded Corroded Classified Positive

HNO3 red fuming (UN2032) Not corroded Not corroded

Not classified Positive

Hydrochloric acid (diluted)

(UN1789)

Corroded Corroded Classified Negative

NaOH solutions (UN1824) Not corroded Corroded Classified Positive

19

2.16.7.1. Example of metal specimen plates after exposure to a corrosive 20

mixture 21

Figure 2.16.7—a Example of corroded metal plates after testing according to UN Test C.1 for a 22 classified mixture 23

24

168



1

This example shows that the corrosion may develop at different rates according to the accurate 2

position of the specimen related to the corroding mixture (sunk in the liquid, placed in the gas 3

phase above liquid or at the liquid/gas interface). 4


ASTM G31-72(2004) Standard Practice for Laboratory Immersion Corrosion Testing of Metals. 6

Jones, D.A., Principles and Prevention of Corrosion, 2nd edition, 1996, Prentice Hall, Upper 7

Saddle River, NJ. ISBN 0-13-359993-0 Page 50-52. 8

DIN 50905-1: 2007, Corrosion of metals - Corrosion testing - Part 1: General guidance 9

(Korrosion der Metalle - Korrosionsuntersuchungen - Teil 1: Grundsätze). 10

Plate located in the liquid phase

Plate located in the interface

Plate located in the

vapour phase



3. PART 3: HEALTH HAZARDS 1

2

[See separate document for specific sections of Part 3 under consultation] 3

3.1. ACUTE TOXICITY 4

5

170



3.2. SKIN CORROSION/IRRITATION 1

2



3.3. SERIOUS EYE DAMAGE/EYE IRRITATION 1

2

3

172



3.4. RESPIRATORY OR SKIN SENSITISATION 1

2



3.5. GERM CELL MUTAGENICITY 1

2

174



3.6. CARCINOGENICITY 1

2



3.7. REPRODUCTIVE TOXICITY 1

3.8. SPECIFIC TARGET ORGAN TOXICITY – SINGLE EXPOSURE (STOT-2

SE) 3

3.9. SPECIFIC TARGET ORGAN TOXICITY – REPEATED EXPOSURE 4

(STOT-RE) 5

6

176



4. PART 4: ENVIRONMENTAL HAZARDS 1

2

[Please note, Part 4 is not under consultation] 3

4

4.1. HAZARDOUS TO THE AQUATIC ENVIRONMENT 5

6



5. PART 5: ADDITIONAL HAZARDS 1

2

[Please note, Part 5 is not under consultation] 3

4

5.1. HAZARDOUS TO THE OZONE LAYER 5

6

ANNEXES 7

8

[Please note, Annexes are not under consultation] 9

10

I ANNEX I: AQUATIC TOXICITY 11

12

178



II ANNEX II: RAPID DEGRADATION 1

2



III ANNEX III: BIOACCUMULATION 1

2

180



IV ANNEX IV: METALS AND INORGANIC METAL COMPOUNDS 1

2



V ANNEX V: COLLECTION OF INTERNET LINKS FOR THE 1

USERS OF THE GUIDANCE 2

3

4

5



VI ANNEX VI: BACKGROUND DOCUMENT TO THE GUIDANCE FOR SETTING SPECIFIC CONCENTRATION LIMITS FOR SUBSTANCES CLASSIFIED FOR REPRODUCTIVE TOXICITY ACCORDING TO REGULATION (EC) NO 1272/2008

EUROPEAN CHEMICALS AGENCY

ANNANKATU 18, P.O. BOX 400,

FI-00121 HELSINKI, FINLAND

ECHA.EUROPA.EU

Guidance on the Application of the CLP Criteria

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Transcript of Guidance on the Application of the CLP Criteria